WO2024078286A1 - Gel composition, and preparation and use thereof - Google Patents

Gel composition, and preparation and use thereof Download PDF

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Publication number
WO2024078286A1
WO2024078286A1 PCT/CN2023/120158 CN2023120158W WO2024078286A1 WO 2024078286 A1 WO2024078286 A1 WO 2024078286A1 CN 2023120158 W CN2023120158 W CN 2023120158W WO 2024078286 A1 WO2024078286 A1 WO 2024078286A1
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Prior art keywords
long
amino acid
chain acyl
gel
acyl amino
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PCT/CN2023/120158
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French (fr)
Chinese (zh)
Inventor
张健
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苏州欧丽特生物医药有限公司
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Publication of WO2024078286A1 publication Critical patent/WO2024078286A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42Amides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/43Guanidines
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64Proteins; Peptides; Derivatives or degradation products thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/14Preparations for removing make-up
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/34Organic compounds containing sulfur

Definitions

  • the present invention relates to the technical field of gel products, and in particular to a gel composition comprising N-long-chain acyl amino acids and basic amino acids/inorganic bases, and related preparation and application in the fields of cosmetics, detergents, toothpastes, etc.
  • Gel-type products are widely used in cosmetics, detergents, toothpaste and other fields because of their clear and transparent/translucent appearance, unique rheological properties, the ability to suspend small particles, a certain degree of ornamental value, and the characteristics of being non-greasy, easy to spread and easy to clean.
  • gel is mainly formed by adding various polymer thickeners or gelling agents.
  • Common thickeners include cellulose, mucopolysaccharides, polyvinyl alcohol, colloids, sodium polyacrylate, polyvinyl pyrrolidone, vinyl polymers, etc.
  • Common varieties include starch, gelatin, sodium alginate, guar gum, chitosan, gum arabic, xanthan gum, soy protein gum, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, modified paraffin resin, carbomer resin, styrene-butadiene rubber, etc.
  • sodium chloride can also be used for thickening.
  • CN107875037A discloses a skin softening gel containing colored wax, which requires the use of acrylic acid (ester)/C10-30 alkyl acrylate cross-linked polymer, and the amount of arginine added in the formula is only 0.2-0.3%, and the arginine is not used to form a gel.
  • CN106361596A discloses an amino acid foaming cleansing gel, which requires the addition of acrylate cross-linked polymers, hydroxyethyl cellulose, etc.
  • hydroxypropyl methylcellulose delays the discharge of water through gelation.
  • JP2021161104A discloses a gel-like hair cosmetic, which contains polyvinyl pyrrolidone as component (A), diglycerol as component (B), arginine as component (C) and xanthan gum as component (D), wherein the arginine is added to give the hair after application a soft and smooth texture.
  • the purpose is to soften the setting force and suppress peeling, and the added amount is only 0.01 mass % or more and less than 0.3 mass %.
  • CN104812373A discloses an oral gel for sensitivity and tooth pain, wherein the gel matrix comprises an anionic polymer and a basic amino acid, wherein the anionic polymer comprises cross-linked poly(acrylic acid).
  • US4010254A discloses a gel based on a vinyl ether-maleic anhydride copolymer neutralized by a basic amino acid.
  • the aqueous solution of the vinyl ether-maleic anhydride copolymer has the property of forming a gel, but the pH value of the aqueous solution is obviously acidic and irritating.
  • the neutralization of the basic amino acid mainly reduces the irritation and does not play a role in the formation of the gel.
  • JP2004123575A discloses a gel component for external use, which mainly utilizes a water-soluble vinyl polymer as a matrix of an aqueous gel, and a basic amino acid (such as arginine) mainly plays a moisturizing role.
  • CN104105686A discloses a gelling agent, which contains a basic amino acid derivative with the following structure.
  • the gelling agent exerts gelling ability in a water system and can be used in various cosmetics.
  • CN104114535B discloses a zwitterionic basic amino acid derivative with the following structure, which can also exert gelation ability in water system.
  • Amino acid surfactants are mild, low toxic, good biodegradability, good wettability, foaming, antistatic, good compatibility and antibacterial properties. They are widely used in the formulation of daily chemicals such as skin care products, shower gels, facial cleansers, detergents and toothpastes, and can also be used in industries such as biomedicine. When amino acid surfactants are used in the formulation, the preparation of gel products will face greater challenges.
  • EP1505954A1 discloses a strong foam cleansing gel containing an acyl amino acid surfactant, wherein the cosmetic cleansing gel contains: a) water at a concentration of 60 to 90% by weight, b) a thickener at a concentration of 0.1 to 5% by weight, and c) an acyl amino acid surfactant at a concentration of 0.1 to 6% by weight.
  • polyacrylate and/or xanthan gum and/or acrylate/alkyl acrylate cross-linked polymer is used as a thickener.
  • CN1798821A discloses a gel composition comprising N-acylamino acid (A) and at least one oily matrix (B).
  • the N-acylamino acid is added in a very small amount (about 5%) to adjust the touch of the oily matrix.
  • amino acid surfactant Although some research has been done, it is still very difficult to thicken the amino acid surfactant system. Related products sometimes have to be used in conjunction with a foaming pump or the amino acid surfactant is not used as the main surfactant, but only as an auxiliary surfactant for traditional petroleum-based surfactants such as fatty alcohol polyoxyethylene ether sulfate (AES), sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.
  • AES fatty alcohol polyoxyethylene ether sulfate
  • sodium dodecyl sulfate sodium dodecylbenzene sulfonate
  • an object of the present invention is to provide a gel composition, wherein the surfactant contained in the composition is mainly an amino acid surfactant.
  • the present invention provides a gel which is transparent/translucent in appearance, mild and non-irritating, and has very good heat and cold resistance.
  • a product it is easy to carry and can be used in various non-home environments such as outdoors; when used, it is very easy to wash.
  • the present invention aims to provide a preparation method with simple process, low cost and easy industrial production, which can easily obtain a gel product based on an amino acid surfactant.
  • the present invention provides a method of imparting gel properties to a cleaning composition.
  • the scheme of the present invention is as follows.
  • a gel composition comprising (a) an N-long-chain acyl amino acid, (b) a basic amino acid, and (c) water, wherein the gel is formed by self-thickening of the N-long-chain acyl amino acid and the basic amino acid;
  • N-long-chain acyl amino acid comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, (c) water, and (d) N-long-chain acyl amino acid dipeptide, and forms a gel through self-thickening of the N-long-chain acyl amino acid, the basic amino acid, and the N-long-chain acyl amino acid dipeptide;
  • the method comprises (a) an N-long-chain acylamino acid, (e) an inorganic base, and (c) water, wherein the gel is formed by self-thickening of the N-long-chain acylamino acid and the inorganic base;
  • it comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, (c) water, and (d) an N-long-chain acyl amino acid dipeptide, and forms a gel through self-thickening of the N-long-chain acyl amino acid, the inorganic base, and the N-long-chain acyl amino acid dipeptide.
  • a gel composition comprising (a) an N-long-chain acyl amino acid, (b) a basic amino acid, and (c) water, wherein the weight percentage of the N-long-chain acyl amino acid is greater than 30 wt%, preferably greater than 33 wt%, more preferably greater than 35 wt%, and the weight percentage of the basic amino acid is greater than 15 wt%, preferably greater than 17 wt%, more preferably greater than 20 wt%;
  • N-long-chain acyl amino acid comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, (c) water, and (d) N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide is greater than 20wt%, preferably greater than 23wt%, and more preferably greater than 20wt%.
  • the weight percentage of basic amino acids is preferably above 25wt%, and the weight percentage of basic amino acids is above 10wt%, preferably above 12wt%, and more preferably above 14wt%;
  • N-long-chain acyl amino acid comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, and (c) water, wherein the weight percentage of N-long-chain acyl amino acid is above 20wt%, preferably above 23wt%, more preferably above 25wt%, and the molar ratio of N-long-chain acyl amino acid to basic amino acid is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
  • a gel composition comprising (a) an N-long-chain acylamino acid, (e) an inorganic base, and (c) water, wherein the weight percentage of the N-long-chain acylamino acid is greater than 40 wt%, preferably greater than 43 wt%, more preferably greater than 45 wt%, and the weight percentage of the inorganic base is greater than 5.5 wt%, preferably greater than 6 wt%, more preferably greater than 6.5 wt%;
  • the N-long-chain acyl amino acid comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, (c) water, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the inorganic base is greater than 4 wt %, preferably greater than 4.5 wt %, more preferably greater than 5 wt %;
  • N-long-chain acyl amino acid comprises (a) N-long-chain acyl amino acid, (e) inorganic base, and (c) water, wherein the weight percentage of N-long-chain acyl amino acid is above 30wt%, preferably above 33wt%, more preferably above 35wt%, and the molar ratio of N-long-chain acyl amino acid to inorganic base is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
  • the amino acids in the N-long-chain acyl amino acids are derived from one or more of glycine, alanine, glutamic acid, sarcosine, aspartic acid, leucine, isoleucine, valine, threonine, proline, phenylalanine, arginine, lysine, and (methyl)taurine.
  • N-long-chain acyl group in the N-long-chain acyl amino acid is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
  • the amino acid in the N-long-chain acylamino acid is derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
  • the N-long-chain acyl amino acid is selected from one or more of cocoyl alanine, lauroyl alanine, lauroyl sarcosine, cocoyl sarcosine, cocoyl glutamic acid, lauroyl glutamic acid, oleoyl glutamic acid, cocoyl glycine, lauroyl glycine and stearoyl glutamic acid, preferably lauroyl alanine, and particularly preferably N-lauroyl-L-alanine.
  • the inorganic base is selected from one or more of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide.
  • the N-long-chain acyl group in the N-long-chain acyl amino acid dipeptide is derived from a saturated or unsaturated straight-chain or branched fatty acid having 8 to 22 carbon atoms; preferably, the N-long-chain acyl group in the N-long-chain acyl amino acid dipeptide is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
  • the amino acid in the N-long-chain acyl amino acid dipeptide is derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably L-alanine.
  • the N-long-chain acyl amino acid dipeptide is selected from one or more of long-chain acyl glycylglycine, long-chain acyl glutamyl glutamate, long-chain acyl alanyl alanine, and long-chain acyl sarcosyl sarcosine.
  • the weight ratio of N-long-chain acyl amino acid to N-long-chain acyl amino acid dipeptide is 20:1 to 1.5:1, preferably 15:1 to 3:1, more preferably 10:1 to 6:1.
  • the basic amino acid or inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acyl amino acid or N-long-chain acyl amino acid dipeptide, preferably with a neutralization degree of 85% or more, more preferably with a neutralization degree of 88% or 90% or more, and less than 100%; preferably, the neutralization degree is 85%-98%, 88%-96%, more preferably 90%-95%.
  • composition is free or substantially free of sodium chloride.
  • the thickener is selected from one or more of cellulose, mucopolysaccharides, polyvinyl alcohols, colloids, sodium polyacrylates, polyvinyl pyrrolidones, and vinyl polymers.
  • the pH value of the gel composition is measured by the dilution method specified in GB/T 13531.1, and the pH value is above 4.5, preferably above 5, and more preferably above 5.5; and the pH value is below 12, preferably below 11, and more preferably below 10.
  • the gel composition according to any one of [1] to [16], after the composition forms a gel, is tested using a Japanese RHEOTECH hardness tester under the test conditions of a load of 2 kg, an adapter of 20 mm ⁇ , a needle penetration speed of 6 cm/min, and a needle penetration distance of 10 mm.
  • the hardness is below 1.80, preferably below 1.50, and more preferably below 1.00.
  • the gel composition according to [18], wherein the water-soluble oil is selected from PEG olive oil esters, PEG isostearates, PEG coconut oil esters, PEG avocado esters.
  • PEG olive oil esters PEG isostearates
  • PEG coconut oil esters PEG avocado esters.
  • PEG-10 olive oil glycerides olive oil PEG-7 esters, olive oil PEG-8 esters, PEG-7 olive oil esters, PEG-15 glyceryl isostearate, PEG-9 coconut oil glycerides, and PEG-11 avocado glycerides.
  • the self-thickening gel is formed based on N-long-chain acyl amino acids, basic amino acids, and N-long-chain acyl amino acid dipeptides;
  • the gel is formed based on the self-thickening of N-long-chain acylamino acids and inorganic bases;
  • the self-thickening gel is formed based on N-long chain acyl amino acids, inorganic bases, and N-long chain acyl amino acid dipeptides.
  • the gel is kept at -8 ⁇ 2°C for 24 hours and can be used normally after returning to room temperature.
  • a toothpaste comprising the gel composition described in any one of [1] to [19].
  • a cosmetic comprising the gel composition described in any one of [1] to [19].
  • a cleaning product comprising the gel composition described in any one of [1] to [19].
  • (b) or (e) is first mixed with (c) to obtain solution I, and then heated at 75-90°C, preferably (a) and optionally (d) are melted at 80-85°C to obtain solution II. Finally, solution I is mixed with solution II at 75-90°C, preferably 80-85°C.
  • a method for imparting gel properties to a cleaning composition comprising (a) an N-long-chain acyl amino acid, and (b) a basic amino acid, wherein the weight percentage of the N-long-chain acyl amino acid is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the basic amino acid is greater than 15 wt %, preferably greater than 17 wt %, more preferably greater than 20 wt %;
  • the cleaning composition comprises (a) an N-long-chain acyl amino acid, (b) a basic amino acid, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 20 wt %, preferably greater than 23 wt %, more preferably greater than 25 wt %, and the weight percentage of the basic amino acid is greater than 10 wt %, preferably greater than 12 wt %, more preferably greater than 14 wt %;
  • the cleaning composition comprises (a) an N-long-chain acyl amino acid and (b) a basic amino acid, wherein the weight percentage of the N-long-chain acyl amino acid is above 20 wt %, preferably above 23 wt %, more preferably above 25 wt %, and the molar ratio of the N-long-chain acyl amino acid to the basic amino acid is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
  • a method for imparting gel properties to a cleaning composition comprising (a) an N-long-chain acylamino acid, and (e) an inorganic base, wherein the weight percentage of the N-long-chain acylamino acid is greater than 40 wt %, preferably greater than 43 wt %, more preferably greater than 45 wt %, and the weight percentage of the inorganic base is greater than 5.5 wt %, preferably greater than 6 wt %, more preferably greater than 6.5 wt %;
  • the cleaning composition comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the inorganic base is greater than 4 wt %, preferably greater than 4.5 wt %, more preferably greater than 5 wt %;
  • the cleaning composition comprises (a) an N-long-chain acyl amino acid and (e) an inorganic base, wherein the weight percentage of the N-long-chain acyl amino acid is above 30 wt %, preferably above 33 wt %, more preferably above 35 wt %, and the molar ratio of the N-long-chain acyl amino acid to the inorganic base is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
  • N-long-chain acyl group in the N-long-chain acyl amino acid is selected from octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearyl, styroyl, styroyl, linoleyl, styro ...
  • fatty acyl coconut oil fatty acyl, palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, most preferably lauroyl;
  • the amino acid in the N-long-chain acylamino acid is derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
  • the inorganic base is selected from one or more of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide.
  • N-long-chain acyl group in the N-long-chain acyl amino acid dipeptide is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
  • the amino acids in the N-long-chain acyl amino acid dipeptide are derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
  • the N-long-chain acyl amino acid dipeptide is selected from one or more of long-chain acyl glycylglycine, long-chain acyl glutamyl glutamate, long-chain acyl alanyl alanine, and long-chain acyl sarcosyl sarcosine.
  • the weight percentage of N-long-chain acyl amino acid is less than 55wt%, preferably less than 50wt%, and more preferably less than 45wt%.
  • the weight percentage of N-long-chain acyl amino acid is less than 75wt%, preferably less than 65wt%, and more preferably less than 60wt%.
  • the basic amino acid or inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acyl amino acid or N-long-chain acyl amino acid dipeptide, and the degree of neutralization is preferably above 85%, more preferably above 88% and less than 100%.
  • the composition consists of (a) N-long-chain acyl amino acid, (b) basic amino acid, (c) water and optionally (d) N-long-chain acyl amino acid dipeptide; or, the composition consists of (a) N-long-chain acyl amino acid, (e) inorganic base, (c) water and optionally (d) N-long-chain acyl amino acid dipeptide; or, the composition consists of (a) N-long-chain acyl amino acid, (b) basic amino acid/(e) inorganic base, (c) water and optionally (d) N-long-chain acyl amino acid dipeptide, a preservative and/or a sweetener.
  • the present invention has the following beneficial technical effects:
  • the gel composition/gel product of the present invention uses an amino acid surfactant (component (a)) as the main surfactant/only surfactant, especially when compounded with a basic amino acid (component (b)).
  • the product is green, environmentally friendly, non-toxic and harmless, is very gentle and non-irritating to human skin during use, and can reduce dependence on petroleum-based products.
  • the present invention prepares a gel product without using a traditional thickener/gelling agent, thereby avoiding the influence of the thickener/gelling agent on product performance (color, foam, efficacy, use experience, etc.).
  • N-long-chain acyl amino acid dipeptide can greatly reduce the amount of raw materials used (i.e., a smaller amount of N-long-chain acyl amino acid can be used to form a gel), and can also improve the heat and cold resistance of the gel to a certain extent, and improve the extrusion and truncation performance of the gel.
  • Gel-state cleaning products are easy to carry and are very suitable for various non-home scenarios such as outdoors and supermarkets.
  • the gel formed by compounding (a) N-long-chain acyl amino acid, (b) basic amino acid and optionally (d) N-long-chain acyl amino acid dipeptide is multifunctional and has very good cleaning power. It can be used as a hand washing product, bath product, shampoo product, makeup remover product, and can also be used as toothpaste. Outdoors, it can be used as a cleaning agent for outdoor tableware, etc.
  • FIG1 is the appearance of the gels of Examples 1-7, wherein a to g are the appearance of the gels of Examples 1 to 7, respectively;
  • FIG2 is the appearance of the gels of Examples 8-10, wherein a to c are the appearance of the gels of Examples 8 to 10 respectively (a is the appearance of the gel of Example 8, b is the appearance of the gel of Example 9, and c is the appearance of the gel of Example 10);
  • FIG3 is the appearance of the gel of Example 11-12, wherein a is the appearance of the gel of Example 11, and b is the appearance of the gel of Example 12;
  • FIG4 is the appearance of the gels of Examples 13-15, wherein a to c are the appearance of the gels of Examples 13 to 15, respectively;
  • FIG5 shows the appearance of the gel of Example 16.
  • a gel composition comprising (a) N-long-chain acylamino acid, (b) basic amino acid, and (c) water.
  • the N-long-chain acyl group in the N-long-chain acyl amino acid is derived from a saturated or unsaturated straight-chain or branched fatty acid having 8 to 22 carbon atoms. Further, the N-long-chain acyl group in the N-long-chain acyl amino acid is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl.
  • the amino acids in the N-long chain acyl amino acids are derived from one or more of glycine, alanine, glutamic acid, sarcosine, aspartic acid, leucine, isoleucine, valine, threonine, proline, phenylalanine, arginine, and lysine. Further, the amino acids in the N-long chain acyl amino acids are derived from one or more of alanine, glycine, glutamic acid, sarcosine, One or more of arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
  • N-long-chain acyl (methyl) taurine refers to N-long-chain acyl methyl taurine or N-long-chain acyl taurine.
  • the N-long-chain acyl amino acid can be selected from cocoyl alanine, lauroyl alanine, cocoyl sarcosine, lauroyl sarcosine, lauroyl glutamic acid, cocoyl glutamic acid, oleoyl glutamic acid, cocoyl glycine, lauroyl glycine, stearoyl glutamic acid, etc., preferably lauroyl alanine, lauroyl sarcosine, especially preferably N-lauroyl-L-alanine.
  • Salts of the relevant N-long-chain acyl amino acids can also be selected as starting materials, and those skilled in the art will understand that there is no essential difference between them and the corresponding acids as starting materials, and they belong to equivalent technical features.
  • the synthesis process of N-long-chain acylamino acids can refer to the general synthesis method of N-acylamino acid type surfactants, which can be divided into direct method and indirect method.
  • the direct synthesis method of fatty acid raw materials includes enzyme catalytic synthesis and dehydration condensation.
  • the indirect synthesis method includes fatty acid chloride acylation, fatty nitrile hydrolysis acylation, fatty acid anhydride acylation, amide carbonylation reaction, etc. More preferably, it is prepared by the reaction of fatty acid chloride with the amino group of amino acid (Shotten-Baumann condensation reaction or Shotten-Baumann reaction).
  • a typical preparation process suitable for the present invention is as follows: amino acid and sodium hydroxide are dissolved in water or a mixed solution of water and acetone to obtain an amino acid salt solution; then lauroyl chloride and sodium hydroxide solution are slowly added dropwise to the amino acid salt solution to control the pH of the reaction system, and after the addition is completed, the product is post-treated.
  • Representative methods are disclosed in CN1798821A, US6703517B2, CN102875409B, JPH0570418A, etc.
  • the post-treatment comprises the following steps: mixing the crude N-long-chain acyl amino acid with a solvent, optionally stirring, and controlling the temperature T of the mixed system to be above the melting point of the long-chain fatty acid and below the melting point of the N-long-chain acyl amino acid, wherein the solvent is water or an organic solvent or a mixed solution of water and an organic solvent; after the system is temperature controlled, a solid-liquid separation operation is performed.
  • the relevant methods are disclosed by the inventors in CN202210867760.7 and PCT/CN2022/107270, and the relevant contents are introduced here.
  • the basic amino acid is selected from one or more of arginine, lysine, citrulline, ornithine, creatine, histidine, diaminobutyric acid, and diaminopropionic acid, preferably Arginine and/or lysine are selected, and arginine is most preferred.
  • arginine is beneficial to the heat resistance and cold resistance of the gel product, and the gel is suitable for extrusion;
  • arginine has the ability to promote the deposition of calcium and phosphorus ions on the dentin surface and dentinal tubules, and at the same time has the effect of isolating external stimulation and delaying dentin sensitivity.
  • the basic amino acid salt of N-long-chain acyl amino acid can also be directly added, which is not essentially different from adding components (a) and (b) separately, and is also covered by the scope of protection of the present invention.
  • Component (c) is not particularly limited. Specifically, ion exchange water, distilled water, purified water, river water, well water, natural water, groundwater, city water, hard water, soft water, etc. can be used. One of these can be used, or two or more selected from the above group can be mixed and used. From the viewpoint of storage stability and sanitation of the product of the present invention, ion exchange water, distilled water, purified water are preferred.
  • the weight percentage of component (a) N-long-chain acylamino acid used in this embodiment is above 30wt%, preferably above 31wt%, 32wt%, 33wt%, 34wt%, 35wt%. If the amount is too low, it is difficult to obtain a gel. Unless otherwise specified, the weight percentages in the present invention are relative to the composition.
  • the weight percentage of component (a) N-long-chain acylamino acid is below 55wt%, preferably 54wt%, 53wt%, 52wt%, 51wt%, 50wt%, 49wt%, 48wt%, 47wt%, 46wt%, 45wt%, 44wt%, 43wt%, 42wt%, 41wt%, 40wt% or less. If the dosage is too high, the gel will be too hard, which is not conducive to extrusion and cutting.
  • the weight percentage of the basic amino acid in component (b) is above 15wt%, preferably above 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%.
  • a gel composition comprising (a) N-long-chain acyl amino acid, (b) basic amino acid, and (c) water, wherein the weight percentage of N-long-chain acyl amino acid is above 20wt%, preferably above 23wt%, and more preferably above 25wt%.
  • Components (a), (b), and (c) refer to the relevant descriptions in other embodiments.
  • the basic amino acid is present in an amount sufficient to partially or completely neutralize the N-long-chain acylamino acid.
  • the degree of neutralization is above 85%, more preferably above 88%.
  • the degree of neutralization is 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%.
  • the molar ratio of N-long chain acyl amino acid to basic amino acid is 1: 0.98 to 1: 0.85, preferably 1: 0.96 to 1: 0.88, more preferably 1: 0.95 to 1: 0.90.
  • the basic amino acid is 0.98, 0.97, 0.96, 0.95, 0.94, 0.93, 0.92, 0.91, 0.90, 0.89, 0.88, 0.87, 0.86 or 0.85 mol.
  • the present invention surprisingly found that when the degree of neutralization is above 85% and less than 100%, a small amount of unneutralized N-long-chain acyl amino acids and/or N-long-chain acyl amino acid dipeptides are contained in the composition system, which can greatly reduce the amount of raw materials used, make the gel softer, and improve the extrusion and truncation performance of the gel.
  • a small amount of unneutralized N-long-chain acyl amino acids and/or N-long-chain acyl amino acid dipeptides are contained in the composition system, which can greatly reduce the amount of raw materials used, make the gel softer, and improve the extrusion and truncation performance of the gel.
  • too much N-long-chain acyl amino acids and/or N-long-chain acyl amino acid dipeptides remain, it will have an adverse effect on the stability of the system, and too much N-long-chain acyl amino acids may gradually precipitate or appear whitening during the use of the product.
  • a gel composition which comprises (a) an N-long-chain acyl amino acid, (b) a basic amino acid, (c) water, and (d) an N-long-chain acyl amino acid dipeptide.
  • N-long-chain acyl amino acid dipeptide is a known concept, and long-chain acyl amino acid dipeptide refers to long-chain acylaminoacyl amino acids, typically long-chain acyl glycyl glycine, long-chain acyl glutamyl glutamic acid, long-chain acyl alanyl alanine, long-chain acyl sarcosyl sarcosine, etc., for example, see CN100448968C, PCT/CN2022/107270, etc.
  • N-long-chain acyl amino acid dipeptide can be prepared from acyl chloride derived from N-long-chain acyl amino acid and amino acid by Schotten-Bowman reaction, etc.; or by reacting amino acid dipeptide such as glutamylglutamic acid with acyl chloride.
  • it is obtained by the relevant preparation method disclosed in PCT/CN2022/107270, and the relevant content is introduced here.
  • the N-long-chain acyl group in the N-long-chain acyl amino acid dipeptide is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
  • the amino acid in the N-long-chain acyl amino acid dipeptide is derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl) taurine, preferably L-alanine.
  • the present invention preferably uses N-long-chain acyl-L-alanine dipeptide, especially lauroyl alanyl alanine.
  • N-long-chain acyl amino acid dipeptide can greatly reduce the amount of raw materials used (i.e., a smaller amount of N-long-chain acyl amino acid can be used to form a gel), and can also improve the heat resistance and cold resistance of the gel to a certain extent, and improve the extrusion and truncation performance of the gel.
  • the total weight percentage of N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide is above 20wt%, preferably above 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%. If the dosage is too low, it is difficult to obtain a gel.
  • the specific amount added is mainly adjusted according to the content of N-long-chain acyl amino acid dipeptide. The higher the content of N-long-chain acyl amino acid dipeptide, the lower the total weight percentage of the corresponding N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide.
  • the weight percentage of N-long-chain acyl amino acid dipeptide is above 0.5wt%, preferably above 0.75wt%, 1wt%, 1.5wt%, 2wt%.
  • the weight ratio of N-long chain acyl amino acid to N-long chain acyl amino acid dipeptide is 20: 1 to 1.5: 1, preferably 15: 1 to 3: 1, more preferably 10: 1 to 6: 1.
  • the weight ratio of N-long chain acyl amino acid to N-long chain acyl amino acid dipeptide is, for example, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3.
  • the weight percentage of component (a) N-long-chain acylamino acid is below 55wt%, preferably 54wt%, 53wt%, 52wt%, 51wt%, 50wt%, 49wt%, 48wt%, 47wt%, 46wt%, 45wt%, 44wt%, 43wt%, 42wt%, 41wt%, 40wt% or less. If the dosage is too high, the gel will be too hard, which is not conducive to extrusion and cutting.
  • the weight percentage of the basic amino acid of component (b) is above 10wt%, preferably above 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%.
  • the basic amino acid is present in an amount sufficient to partially or completely neutralize the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide, for example, the amount of basic amino acid added in the aforementioned embodiment can be referred to.
  • the degree of neutralization is less than 100% and the composition contains the N-long-chain acyl amino acid dipeptide
  • the amount of raw materials used (referring to the N-long-chain acyl amino acid and dipeptide) can be reduced to a minimum, and the hardness of the product is relatively minimized, which facilitates easier and easier canning of the gel.
  • a gel composition which comprises (a) an N-long-chain acylamino acid, (e) an inorganic base, and (c) water.
  • Components (a) and (c) refer to the relevant descriptions in other embodiments.
  • Component (e) inorganic base is selected from one or more of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide. Generally speaking, conventional sodium hydroxide can be used without special requirements. If sodium hydroxide solution is used, The dosage refers to the dosage of sodium hydroxide, not the dosage of sodium hydroxide solution.
  • the weight percentage of component (a) N-long chain acylamino acid is above 40 wt%, preferably above 43 wt%, more preferably above 45 wt%. If the amount is too low, it is difficult to obtain a gel.
  • the weight percentage of component (a) N-long-chain acylamino acid is below 75wt%, preferably below 70wt%, 68wt%, 65wt%, 64wt%, 63wt%, 62wt%, 61wt%, 60wt%, 59wt%, 58wt%, 57wt%, 56wt%, 55wt%. If the dosage is too high, the gel will be too hard, which is not conducive to extrusion and cutting.
  • the weight percentage of the inorganic base of component (e) is above 5.5 wt%, preferably above 6 wt%, more preferably above 6.5 wt%.
  • the inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acylamino acid.
  • a gel composition which comprises (a) N-long-chain acylamino acid, (e) inorganic base, and (c) water, wherein the weight percentage of the N-long-chain acylamino acid is greater than 30 wt%, preferably greater than 33 wt%, and more preferably greater than 35 wt%.
  • the inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acylamino acid.
  • the degree of neutralization is above 85%, more preferably above 88%.
  • the degree of neutralization is 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%.
  • the molar ratio of N-long chain acyl amino acid to inorganic base is 1: 0.98 to 1: 0.85, preferably 1: 0.96 to 1: 0.88, more preferably 1: 0.95 to 1: 0.90.
  • the inorganic base is 0.98, 0.97, 0.96, 0.95, 0.94, 0.93, 0.92, 0.91, 0.90, 0.89, 0.88, 0.87, 0.86 or 0.85 mol.
  • the present invention unexpectedly discovered that when the degree of neutralization is above 85% and less than 100%, a small amount of N-long-chain acyl amino acid and/or N-long-chain acyl amino acid dipeptide is contained in the composition system, which can greatly reduce the amount of raw materials used, make the gel softer, and improve the extrusion and cutting performance of the gel.
  • a gel composition comprising (a) N- Long-chain acyl amino acid, (e) inorganic base, (c) water, (d) N-long-chain acyl amino acid dipeptide.
  • Components (a), (e), (c), (d) refer to the relevant descriptions in other embodiments.
  • N-long-chain acyl amino acid dipeptide can greatly reduce the amount of raw materials used (i.e., a smaller amount of N-long-chain acyl amino acid can be used to form a gel), and can also improve the heat and cold resistance of the gel to a certain extent, and improve the extrusion and truncation performance of the gel.
  • the total weight percentage of N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide is above 30wt%, preferably above 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%. If the dosage is too low, it is difficult to obtain a gel.
  • the specific amount added is mainly adjusted according to the content of N-long-chain acyl amino acid dipeptide. The higher the content of N-long-chain acyl amino acid dipeptide, the lower the total weight percentage of the corresponding N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide.
  • the weight percentage of N-long-chain acyl amino acid dipeptide is above 0.5wt%, preferably above 0.75wt%, 1wt%, 1.5wt%, 2wt%.
  • the weight ratio of N-long chain acyl amino acid to N-long chain acyl amino acid dipeptide is 20: 1 to 1.5: 1, preferably 15: 1 to 3: 1, more preferably 10: 1 to 6: 1.
  • the weight ratio of N-long chain acyl amino acid to N-long chain acyl amino acid dipeptide is, for example, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3.
  • the weight percentage of component (a) N-long-chain acylamino acid is below 75wt%, preferably below 70wt%, 68wt%, 65wt%, 64wt%, 63wt%, 62wt%, 61wt%, 60wt%, 59wt%, 58wt%, 57wt%, 56wt%, 55wt%. If the dosage is too high, the gel will be too hard, which is not conducive to extrusion and cutting.
  • the weight percentage of component (e) inorganic base is above 4wt%, preferably above 4.5wt%, more preferably above 5wt%.
  • the inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acylamino acid and the N-long-chain acylamino acid dipeptide.
  • the composition of the present invention contains no or substantially no thickener.
  • substantially no it is meant that the amount of thickener in the composition does not significantly affect the performance of the product, and the amount of thickener is insufficient to form a gel, i.e., the gel formation of the present invention is not due to the action of the thickener.
  • the composition of the present invention does not contain any traditional thickener at all. As described in the technical specification, traditional thickeners/gelling agents have adverse effects on product performance (color, foam, efficacy, user experience, etc.).
  • composition of the present invention does not contain thickeners such as cellulose, mucopolysaccharides, polyvinyl alcohols, colloids, sodium polyacrylates, polyvinyl pyrrolidones, vinyl polymers, etc.
  • thickeners such as cellulose, mucopolysaccharides, polyvinyl alcohols, colloids, sodium polyacrylates, polyvinyl pyrrolidones, vinyl polymers, etc.
  • the composition of the present invention does not contain starch, gelatin, sodium alginate, guar gum, chitosan, gum arabic, xanthan gum, soy protein gum, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, modified paraffin resin, carbomer resin, styrene-butadiene rubber, etc.
  • composition of the present invention does not involve an AES system and does not require sodium chloride thickening, so the composition does not contain or substantially contains no sodium chloride.
  • substantially contains no means that the amount of sodium chloride in the composition will not significantly affect the performance of the product, and the amount of sodium chloride is insufficient to form a gel.
  • the pH value of the gel composition of the present invention falls within the range of weak acidity to weak alkalinity, which is advantageous for application.
  • the pH value of the gel composition is measured by the dilution method specified in GB/T 13531.1, and the pH value is above 4.5, preferably above 5, and more preferably above 5.5; and the pH value is below 12, preferably below 11, and more preferably below 10.
  • the hardness is tested by a Japanese RHEOTECH hardness tester under the test conditions of a load of 2 kg, an adapter of 20 mm ⁇ , a needle penetration speed of 6 cm/min, and a needle penetration distance of 10 mm.
  • the hardness is below 1.80, preferably below 1.70, 1.60, 1.50, 1.40, 1.30, 1.20, 1.10 or 1.00, and more preferably below 0.90, 0.80, 0.70, 0.50, 0.40, 0.30 or 0.20.
  • the present invention also provides a gel, which is prepared from the above-mentioned gel composition.
  • the gel of the present invention has good heat resistance and cold resistance.
  • the gel is kept at 40 ⁇ 1°C for 24 hours and can be used normally after returning to room temperature; the gel is kept at -8 ⁇ 2°C for 24 hours and can be used normally after returning to room temperature.
  • the "can be used normally” means that the appearance and performance of the gel have no obvious changes and do not affect the use.
  • the gel of the present invention can be used as a cleansing gel, a skin care gel, a shampoo gel, a shaving gel, a makeup removal gel, a massage gel, a cosmetic gel, an oral gel or a multifunctional gel.
  • the multifunctionality means that it can be used in a variety of scenarios and has a variety of uses. For example, it can be used as a hand washing product, a bath product, a shampoo product, a makeup removal product, or a multifunctional gel. It can be used as toothpaste; outdoors, it can be used as a cleaner for various utensils such as outdoor tableware.
  • the present invention also provides a toothpaste containing the aforementioned gel composition.
  • a toothpaste product abrasives, moisturizers, sweeteners, flavors, preservatives, colorants, etc. may also be added according to the requirements of product performance.
  • the present invention also provides a cosmetic comprising the aforementioned gel composition.
  • a cosmetic product moisturizers, flavors, preservatives, colorants, oils, suspended particles, etc. may also be added according to the requirements of product performance.
  • the suspended particles are selected from oil-insoluble solid particles or oil-immiscible liquids.
  • the oil-insoluble solid particles include mica, starch, zinc oxide, titanium dioxide, talc and silicone elastomer.
  • the oil-immiscible liquid includes glycerin, water and polyols.
  • the present invention also provides a cleaning product, which contains the aforementioned gel composition.
  • a cleaning product which contains the aforementioned gel composition.
  • softeners, chelating agents, preservatives, glycerin and essences can also be added according to the requirements of product performance.
  • the present invention also provides a cleaning product with a minimal formula, which contains only the aforementioned (a) N-long-chain acyl amino acid, (b) basic amino acid/(e) inorganic base, and (c) water. Alternatively, it contains only the aforementioned (a) N-long-chain acyl amino acid, (b) basic amino acid/(e) inorganic base, (c) water and necessary preservatives and/or sweeteners.
  • the present invention provides a method for preparing a gel composition, comprising the following steps: mixing (a), (b) or (e), (c) and optionally (d) at 75-90°C, preferably 80-85°C.
  • (b) or (e) is first mixed with (c) to obtain solution I, then (a) and optional (d) are melted at 75-90°C, preferably 80-85°C to obtain solution II, and finally, solution I is mixed with solution II at 75-90°C, preferably 80-85°C.
  • the present invention also provides a method for imparting gel properties to a cleaning composition, the cleaning composition comprising (a) an N-long-chain acyl amino acid, and (b) a basic amino acid, wherein the weight percentage of the N-long-chain acyl amino acid is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the basic amino acid is greater than 15 wt %, preferably greater than 17 wt %, more preferably greater than 20 wt %;
  • the invention comprises (a) an N-long chain acyl amino acid, (b) a basic amino acid, and (d) an N-long chain acyl amino acid dipeptide, wherein the N-long chain acyl amino acid and the N-long chain acyl amino acid dipeptide
  • the total weight percentage of is more than 20wt%, preferably more than 23wt%, more preferably more than 25wt%
  • the weight percentage of basic amino acids is more than 10wt%, preferably more than 12wt%, more preferably more than 14wt%;
  • the cleaning composition comprises (a) an N-long-chain acyl amino acid and (b) a basic amino acid, wherein the weight percentage of the N-long-chain acyl amino acid is above 20 wt %, preferably above 23 wt %, more preferably above 25 wt %, and the molar ratio of the N-long-chain acyl amino acid to the basic amino acid is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
  • Components (a), (b), (d) and their amounts are as described in other embodiments. When the above components are used, gel properties can be imparted to the cleaning composition.
  • the present invention also provides another method for imparting gel properties to a cleaning composition, the cleaning composition comprising (a) an N-long-chain acylamino acid, and (e) an inorganic base, wherein the weight percentage of the N-long-chain acylamino acid is greater than 40 wt %, preferably greater than 43 wt %, more preferably greater than 45 wt %, and the weight percentage of the inorganic base is greater than 5.5 wt %, preferably greater than 6 wt %, more preferably greater than 6.5 wt %;
  • the N-long-chain acyl amino acid comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the inorganic base is greater than 4 wt %, preferably greater than 4.5 wt %, more preferably greater than 5 wt %;
  • the cleaning composition comprises (a) an N-long-chain acyl amino acid and (e) an inorganic base, wherein the weight percentage of the N-long-chain acyl amino acid is above 30 wt %, preferably above 33 wt %, more preferably above 35 wt %, and the molar ratio of the N-long-chain acyl amino acid to the inorganic base is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
  • Components (a), (e), (d) and their usage amounts refer to the related descriptions in other embodiments.
  • gel properties can be imparted to the cleaning composition.
  • a gel can also be formed.
  • a gel can be formed when the total content of N-lauroyl-L-alanine and dipeptide is 25 wt %.
  • Example (VI) except for N-lauroyl-L-alanine and arginine, the balance is water, and the molar ratio refers to N- Lauroyl-L-Alanine:Arginine. *5.
  • the composition of the long-chain acyl amino acid in Example 20 is: 95% N-lauroyl-L-alanine + 5% lauroyl alanine dipeptide.
  • Test instrument Japan RHEOTECH hardness tester/rheometer, test conditions: load 2kg (select 2K/20N), adapter 20mm ⁇ , needle penetration speed 6cm/min, needle penetration distance 10mm.
  • Heat resistance test maintain at 40°C for 24h, 60°C, 70°C, 80°C for 1h respectively, then return to room temperature to observe the stability of the gel under high temperature conditions and whether it can be used normally after returning to room temperature.
  • Cold resistance test keep at -6°C for 24h, keep at -18°C for 12h, then return to room temperature to observe the stability of the gel under low temperature conditions and whether it can be used normally after returning to room temperature.
  • Stability test -6°C, 50°C, cycle test, light resistance test were performed for one month and then stopped for observation.
  • Cycle test 0°C ⁇ 2 days ⁇ 25°C ⁇ 2 days ⁇ 40°C ⁇ 2 days cycle;
  • light resistance test fluorescent light irradiation conditions: about 23000Lux/day, 25°C.
  • the combination of N-long-chain acyl amino acids and arginine has very good stability.
  • the combination of N-lauroyl-L-alanine and arginine performs well in heat resistance, cold resistance, stability, and excellent cleaning power; the combination of lauroyl sarcosine and arginine performs well in heat resistance, cold resistance, and stability, but lacks cleaning power.
  • N-lauroyl-L-alanine and lysine has poor stability (especially low temperature stability); the combination of N-lauroyl-L-alanine and sodium hydroxide has moderate stability.
  • N-lauroyl-L-alanine lauroyl alanyl alanine (dipeptide) and arginine has the best performance.
  • the product has excellent performance in heat resistance, cold resistance and stability; on the other hand, its high cleaning power is conducive to use in various scenarios.
  • the degree of neutralization when the degree of neutralization is above 85% and less than 100%, the gel formed is very soft and more suitable for filling tubular products.
  • the degree of neutralization is low (such as below 85%), it is found that whitening sometimes occurs in the heat and cold cycle test (it may be that the excessive unneutralized lauroyl alanine will gradually precipitate).
  • a small amount of dipeptide is added and not completely neutralized (Example 20)
  • a stable soft gel can be formed using about 25% of long-chain acyl amino acids.

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Abstract

Disclosed in the present invention are a gel composition, a related gel, and a preparation method therefor and the use thereof. The gel composition is based on a long-chain N-acyl amino acid, contains no thickener, is transparent/semitransparent in appearance, is mild and non-irritant, and has very good heat resistance and cold resistance. A related gel product is convenient to carry and applicable to various environments and various usage scenarios, and is very easy to rinse off after use. The gel composition provided in the present invention can be applied to a cleaning composition, a washing composition, a cosmetic composition, a skin care composition, a toothpaste composition, etc.

Description

凝胶组合物及其制备和应用Gel composition and its preparation and application 技术领域Technical Field
本发明涉及凝胶产品技术领域,特别涉及包含N-长链酰基氨基酸和碱性氨基酸/无机碱的凝胶组合物,以及相关的制备和在化妆品、清洁剂、牙膏等领域的应用。The present invention relates to the technical field of gel products, and in particular to a gel composition comprising N-long-chain acyl amino acids and basic amino acids/inorganic bases, and related preparation and application in the fields of cosmetics, detergents, toothpastes, etc.
背景技术Background technique
凝胶型产品由于外观清彻透明/半透明,具有特有的流变性能,可悬浮小颗粒,具有一定观赏性以及使用时无油腻感、易涂展、易清洗等特点,广泛应用于化妆品、清洁剂、牙膏等领域。Gel-type products are widely used in cosmetics, detergents, toothpaste and other fields because of their clear and transparent/translucent appearance, unique rheological properties, the ability to suspend small particles, a certain degree of ornamental value, and the characteristics of being non-greasy, easy to spread and easy to clean.
目前,主要是通过添加各种高分子增稠剂或凝胶化剂来形成凝胶。常用的增稠剂有纤维素类、粘多糖类、聚乙烯醇类、胶质类、聚丙烯酸钠类、聚乙烯基吡咯烷酮类、乙烯基聚合物类等。常用品种有淀粉、明胶、海藻酸钠、瓜尔胶、甲壳胶、阿拉伯树胶、黄原胶、大豆蛋白胶、聚丙烯酰胺、聚乙烯醇、聚乙烯吡咯烷酮、改性石蜡树脂、卡波树脂、丁苯橡胶等。对于AES体系,则还可以使用氯化钠增稠。At present, gel is mainly formed by adding various polymer thickeners or gelling agents. Common thickeners include cellulose, mucopolysaccharides, polyvinyl alcohol, colloids, sodium polyacrylate, polyvinyl pyrrolidone, vinyl polymers, etc. Common varieties include starch, gelatin, sodium alginate, guar gum, chitosan, gum arabic, xanthan gum, soy protein gum, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, modified paraffin resin, carbomer resin, styrene-butadiene rubber, etc. For AES system, sodium chloride can also be used for thickening.
CN107875037A公开了一种含彩蜡的柔肤啫喱,需要使用丙烯酸(酯)类/C10-30烷醇丙烯酸酯交联聚合物,配方中的精氨酸加入量仅为0.2-0.3%,且精氨酸并非用于形成凝胶。CN107875037A discloses a skin softening gel containing colored wax, which requires the use of acrylic acid (ester)/C10-30 alkyl acrylate cross-linked polymer, and the amount of arginine added in the formula is only 0.2-0.3%, and the arginine is not used to form a gel.
CN106361596A公开了一种氨基酸发泡洁面啫喱,配方中需要加入丙烯酸酯类交联聚合物、羟乙基纤维素等,在表面活性剂体系中,羟丙基甲基纤维素通过凝胶化来延缓水分的排出。CN106361596A discloses an amino acid foaming cleansing gel, which requires the addition of acrylate cross-linked polymers, hydroxyethyl cellulose, etc. In the surfactant system, hydroxypropyl methylcellulose delays the discharge of water through gelation.
JP2021161104A公开了一种啫喱状美发化妆品,通过含有聚乙烯吡咯烷酮作为成分(A),双甘油作为成分(B),精氨酸作为成分(C)黄原胶作为成分(D),其中,精氨酸的加入是以赋予涂布后的毛发柔 软的定型力并抑制剥落为目的,加入量也仅有0.01质量%以上且小于0.3质量%。JP2021161104A discloses a gel-like hair cosmetic, which contains polyvinyl pyrrolidone as component (A), diglycerol as component (B), arginine as component (C) and xanthan gum as component (D), wherein the arginine is added to give the hair after application a soft and smooth texture. The purpose is to soften the setting force and suppress peeling, and the added amount is only 0.01 mass % or more and less than 0.3 mass %.
CN104812373A公开了一种用于敏感性和牙齿疼痛的口用凝胶,凝胶基质包含阴离子聚合物和碱性氨基酸,阴离子聚合物包含交联的聚(丙烯酸)。CN104812373A discloses an oral gel for sensitivity and tooth pain, wherein the gel matrix comprises an anionic polymer and a basic amino acid, wherein the anionic polymer comprises cross-linked poly(acrylic acid).
US4010254A公开了基于被碱性氨基酸中和的乙烯基醚-马来酸酐共聚物的凝胶,乙烯基醚马来酸酐共聚物的水溶液具有形成凝胶的特性,但其水溶液的pH值明显呈酸性,具有刺激性。碱性氨基酸的中和主要是降低刺激作用,对凝胶的形成并不起作用。US4010254A discloses a gel based on a vinyl ether-maleic anhydride copolymer neutralized by a basic amino acid. The aqueous solution of the vinyl ether-maleic anhydride copolymer has the property of forming a gel, but the pH value of the aqueous solution is obviously acidic and irritating. The neutralization of the basic amino acid mainly reduces the irritation and does not play a role in the formation of the gel.
JP2004123575A公开了一种外用凝胶成分,主要是利用水溶性乙烯基聚合物作为水性凝胶剂的基质,而碱性氨基酸(如精氨酸)主要起保湿作用。JP2004123575A discloses a gel component for external use, which mainly utilizes a water-soluble vinyl polymer as a matrix of an aqueous gel, and a basic amino acid (such as arginine) mainly plays a moisturizing role.
上述文献,均采用常规凝胶形成思路,主要采用高分子增稠剂来制备凝胶,碱性氨基酸的加入量很少,也不起凝胶作用。常规的凝胶体系仍然存在很多问题。例如在存在盐的系统中,有时用高分子增稠剂较难使产品凝胶化,需要添加大量的水溶性高分子增稠剂,这对产品的功能性产生不利影响,对使用感受如肤感等也是不利的。又例如增稠剂/凝胶化剂的加入,有时在高温会出现变色现象;表面活性剂的泡沫特性被抑制;清洁时肤感被高分子影响,假滑、清洗不净、残留感强烈等。The above documents all adopt the conventional gel formation idea, mainly using polymer thickeners to prepare gels. The amount of basic amino acids added is very small and does not play a gel role. Conventional gel systems still have many problems. For example, in a system with salt, it is sometimes difficult to gel the product with a polymer thickener, and a large amount of water-soluble polymer thickener needs to be added, which has an adverse effect on the functionality of the product and is also detrimental to the user experience such as skin feel. For example, the addition of thickeners/gelling agents sometimes causes discoloration at high temperatures; the foaming properties of surfactants are suppressed; the skin feel is affected by the polymer during cleaning, resulting in false slipperiness, incomplete cleaning, and a strong residual feeling.
CN104105686A公开了一种凝胶化剂,其含有如下结构的碱性氨基酸衍生物,该凝胶化剂在水系中发挥凝胶化能力,可以用于各类化妆品中。
CN104105686A discloses a gelling agent, which contains a basic amino acid derivative with the following structure. The gelling agent exerts gelling ability in a water system and can be used in various cosmetics.
CN104114535B公开了一种如下结构的两性离子型碱性氨基酸衍生物,同样能够在水系中发挥凝胶化能力。
CN104114535B discloses a zwitterionic basic amino acid derivative with the following structure, which can also exert gelation ability in water system.
上述文献使用氨基酸衍生物作为凝胶化剂,但其依赖于氨基酸衍生物的特殊结构,成本也较高,不利于大规模推广使用。The above-mentioned documents use amino acid derivatives as gelling agents, but they rely on the special structure of amino acid derivatives and are also costly, which is not conducive to large-scale promotion and use.
氨基酸表面活性剂具有温和、低毒、良好的生物降解性、良好的润湿性、起泡性、抗静电性、较好的配伍性及抗菌性等特点,广泛应用于护肤品、沐浴露、洗面奶、洗涤剂和牙膏等日用化学品配方中,还可用于生物医药等行业中。当配方中使用氨基酸表面活性剂,在制备凝胶产品时将面临更大的挑战。Amino acid surfactants are mild, low toxic, good biodegradability, good wettability, foaming, antistatic, good compatibility and antibacterial properties. They are widely used in the formulation of daily chemicals such as skin care products, shower gels, facial cleansers, detergents and toothpastes, and can also be used in industries such as biomedicine. When amino acid surfactants are used in the formulation, the preparation of gel products will face greater challenges.
针对包含氨基酸表面活性剂的凝胶产品,已经开展了一些研究,例如EP1505954A1公开了含有酰基氨基酸表面活性剂的强泡沫清洁凝胶,该化妆品清洁凝胶包含:a)浓度为60至90%重量的水,b)浓度为0.1至5%重量的增稠剂,c)浓度为0.1至6重量%的酰基氨基酸表面活性剂。为了形成凝胶,其将聚丙烯酸酯和/或黄原胶和/或丙烯酸酯/丙烯酸烷基酯交联聚合物用作增稠剂。Some research has been conducted on gel products containing amino acid surfactants. For example, EP1505954A1 discloses a strong foam cleansing gel containing an acyl amino acid surfactant, wherein the cosmetic cleansing gel contains: a) water at a concentration of 60 to 90% by weight, b) a thickener at a concentration of 0.1 to 5% by weight, and c) an acyl amino acid surfactant at a concentration of 0.1 to 6% by weight. In order to form the gel, polyacrylate and/or xanthan gum and/or acrylate/alkyl acrylate cross-linked polymer is used as a thickener.
CN1798821A公开了一种凝胶状组合物,含有N-酰基氨基酸(A)和至少1种油性基质(B),N-酰基氨基酸加入量很少(5%左右),起到调节油性基质触感的作用。CN1798821A discloses a gel composition comprising N-acylamino acid (A) and at least one oily matrix (B). The N-acylamino acid is added in a very small amount (about 5%) to adjust the touch of the oily matrix.
虽然已经有了一定的研究,但是氨基酸表面活性剂体系增稠仍然非常困难,相关产品有时不得不配合发泡泵使用或者不将氨基酸表面活性剂作为主表面活性剂,仅作为传统的脂肪醇聚氧乙烯醚硫酸盐(AES)、十二烷基硫酸钠、十二烷基苯磺酸钠等石油基表面活性剂的辅助表面活性剂。Although some research has been done, it is still very difficult to thicken the amino acid surfactant system. Related products sometimes have to be used in conjunction with a foaming pump or the amino acid surfactant is not used as the main surfactant, but only as an auxiliary surfactant for traditional petroleum-based surfactants such as fatty alcohol polyoxyethylene ether sulfate (AES), sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.
开发高质量多功能环境友好型表面活性剂已成为表面活性剂工业的主要方向,氨基酸表面活性剂替代传统石油基表面活性剂是行业发展的趋势。联合利华已经宣布到2025年将石油基产品的使用量减半,2030年将石油基产品的使用量归零。因此,非常有必要解决氨基酸表面活性剂作为主表面活性剂时,相应凝胶产品的制备问题。尤其是在不使用传统增稠剂/凝胶化剂的情况下,制备出凝胶产品。 The development of high-quality, multifunctional and environmentally friendly surfactants has become the main direction of the surfactant industry. The use of amino acid surfactants to replace traditional petroleum-based surfactants is the trend of industry development. Unilever has announced that it will halve the use of petroleum-based products by 2025 and return the use of petroleum-based products to zero by 2030. Therefore, it is very necessary to solve the problem of preparing corresponding gel products when amino acid surfactants are used as the main surfactant. In particular, gel products can be prepared without using traditional thickeners/gelling agents.
发明内容Summary of the invention
有鉴于此,一方面,本发明的目的在于提供一种凝胶组合物,该组合物中所包含的表面活性剂以氨基酸表面活性剂为主。In view of this, on one hand, an object of the present invention is to provide a gel composition, wherein the surfactant contained in the composition is mainly an amino acid surfactant.
另一方面,本发明提供一种凝胶,其外观透明/半透明,温和无刺激,具有非常好的耐热及耐寒性。作为产品,其携带方便,可以适用于各种非居家的环境如户外;使用时,非常容易冲洗。On the other hand, the present invention provides a gel which is transparent/translucent in appearance, mild and non-irritating, and has very good heat and cold resistance. As a product, it is easy to carry and can be used in various non-home environments such as outdoors; when used, it is very easy to wash.
再一方面,本发明的目的在于提供一种工艺简单、成本低、易于实现工业化生产的制备方法,该方法能够容易的获得基于氨基酸表面活性剂的凝胶产品。On the other hand, the present invention aims to provide a preparation method with simple process, low cost and easy industrial production, which can easily obtain a gel product based on an amino acid surfactant.
最后一方面,本发明提供一种赋予清洁组合物凝胶特性的方法。In a final aspect, the present invention provides a method of imparting gel properties to a cleaning composition.
具体而言,本发明方案如下。Specifically, the scheme of the present invention is as follows.
[1]一种凝胶组合物,其包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,通过N-长链酰基氨基酸、碱性氨基酸的自增稠形成凝胶;[1] A gel composition comprising (a) an N-long-chain acyl amino acid, (b) a basic amino acid, and (c) water, wherein the gel is formed by self-thickening of the N-long-chain acyl amino acid and the basic amino acid;
或者,包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,(d)N-长链酰基氨基酸二肽,通过N-长链酰基氨基酸、碱性氨基酸、N-长链酰基氨基酸二肽的自增稠形成凝胶;Alternatively, it comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, (c) water, and (d) N-long-chain acyl amino acid dipeptide, and forms a gel through self-thickening of the N-long-chain acyl amino acid, the basic amino acid, and the N-long-chain acyl amino acid dipeptide;
或者,包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,通过N-长链酰基氨基酸、无机碱的自增稠形成凝胶;Alternatively, the method comprises (a) an N-long-chain acylamino acid, (e) an inorganic base, and (c) water, wherein the gel is formed by self-thickening of the N-long-chain acylamino acid and the inorganic base;
或者,包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,(d)N-长链酰基氨基酸二肽,通过N-长链酰基氨基酸、无机碱、N-长链酰基氨基酸二肽的自增稠形成凝胶。Alternatively, it comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, (c) water, and (d) an N-long-chain acyl amino acid dipeptide, and forms a gel through self-thickening of the N-long-chain acyl amino acid, the inorganic base, and the N-long-chain acyl amino acid dipeptide.
[2]一种凝胶组合物,其包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,其中,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上,碱性氨基酸重量百分含量在15wt%以上,优选17wt%以上,更优选20wt%以上;[2] A gel composition comprising (a) an N-long-chain acyl amino acid, (b) a basic amino acid, and (c) water, wherein the weight percentage of the N-long-chain acyl amino acid is greater than 30 wt%, preferably greater than 33 wt%, more preferably greater than 35 wt%, and the weight percentage of the basic amino acid is greater than 15 wt%, preferably greater than 17 wt%, more preferably greater than 20 wt%;
或者,包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在20wt%以上,优选23wt%以上,更优 选25wt%以上,碱性氨基酸重量百分含量在10wt%以上,优选12wt%以上,更优选14wt%以上;Alternatively, it comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, (c) water, and (d) N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide is greater than 20wt%, preferably greater than 23wt%, and more preferably greater than 20wt%. The weight percentage of basic amino acids is preferably above 25wt%, and the weight percentage of basic amino acids is above 10wt%, preferably above 12wt%, and more preferably above 14wt%;
或者,包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,其中,N-长链酰基氨基酸重量百分含量在20wt%以上,优选23wt%以上,更优选25wt%以上,N-长链酰基氨基酸与碱性氨基酸的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。Alternatively, it comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, and (c) water, wherein the weight percentage of N-long-chain acyl amino acid is above 20wt%, preferably above 23wt%, more preferably above 25wt%, and the molar ratio of N-long-chain acyl amino acid to basic amino acid is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
[3]一种凝胶组合物,其包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,其中,N-长链酰基氨基酸重量百分含量在40wt%以上,优选43wt%以上,更优选45wt%以上,无机碱重量百分含量在5.5wt%以上,优选6wt%以上,更优选6.5wt%以上;[3] A gel composition comprising (a) an N-long-chain acylamino acid, (e) an inorganic base, and (c) water, wherein the weight percentage of the N-long-chain acylamino acid is greater than 40 wt%, preferably greater than 43 wt%, more preferably greater than 45 wt%, and the weight percentage of the inorganic base is greater than 5.5 wt%, preferably greater than 6 wt%, more preferably greater than 6.5 wt%;
或者,包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在30wt%以上,优选33wt%以上,更优选35wt%以上,无机碱重量百分含量在4wt%以上,优选4.5wt%以上,更优选5wt%以上;Alternatively, it comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, (c) water, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the inorganic base is greater than 4 wt %, preferably greater than 4.5 wt %, more preferably greater than 5 wt %;
或者,包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,其中,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上,N-长链酰基氨基酸与无机碱的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。Alternatively, it comprises (a) N-long-chain acyl amino acid, (e) inorganic base, and (c) water, wherein the weight percentage of N-long-chain acyl amino acid is above 30wt%, preferably above 33wt%, more preferably above 35wt%, and the molar ratio of N-long-chain acyl amino acid to inorganic base is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
[4]根据[1]-[3]任一项所述的凝胶组合物,所述N-长链酰基氨基酸中的N-长链酰基来源于碳原子数8~22的饱和或不饱和直链或支链的脂肪酸;[4] The gel composition according to any one of [1] to [3], wherein the N-long-chain acyl group in the N-long-chain acyl amino acid is derived from a saturated or unsaturated linear or branched fatty acid having 8 to 22 carbon atoms;
和/或,所述N-长链酰基氨基酸中的氨基酸来源于甘氨酸、丙氨酸、谷氨酸、肌氨酸、天冬氨酸、亮氨酸、异亮氨酸、缬氨酸、苏氨酸、脯氨酸、苯丙氨酸、精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种。And/or, the amino acids in the N-long-chain acyl amino acids are derived from one or more of glycine, alanine, glutamic acid, sarcosine, aspartic acid, leucine, isoleucine, valine, threonine, proline, phenylalanine, arginine, lysine, and (methyl)taurine.
[5]根据[1]-[4]任一项所述的凝胶组合物,所述N-长链酰基氨基酸中的N-长链酰基选自辛酰基、癸酰基、十一烷酰基、月桂酰基、肉豆蔻酰基、十五烷酰基、棕榈酰基、硬脂酰基、油酰基、亚油酰基、异硬脂酰基、椰子油脂肪酰基、棕榈油脂肪酰基中的一种或多种,优选椰子油脂肪酰基或月桂酰基,最优选月桂酰基; [5] The gel composition according to any one of [1] to [4], wherein the N-long-chain acyl group in the N-long-chain acyl amino acid is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
和/或,所述N-长链酰基氨基酸中的氨基酸来源于丙氨酸、甘氨酸、谷氨酸、肌氨酸、精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种,优选丙氨酸,最优选L-丙氨酸。And/or, the amino acid in the N-long-chain acylamino acid is derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
[6]根据[1]-[5]任一项所述的凝胶组合物,所述N-长链酰基氨基酸选自椰油酰基丙氨酸、月桂酰基丙氨酸、月桂酰肌氨酸、椰油酰肌氨酸、椰油酰谷氨酸、月桂酰谷氨酸、油酰谷氨酸、椰油酰甘氨酸、月桂酰甘氨酸、硬脂酰谷氨酸中的一种或多种,优选月桂酰基丙氨酸,尤其优选N-月桂酰-L-丙氨酸。[6] According to the gel composition of any one of [1] to [5], the N-long-chain acyl amino acid is selected from one or more of cocoyl alanine, lauroyl alanine, lauroyl sarcosine, cocoyl sarcosine, cocoyl glutamic acid, lauroyl glutamic acid, oleoyl glutamic acid, cocoyl glycine, lauroyl glycine and stearoyl glutamic acid, preferably lauroyl alanine, and particularly preferably N-lauroyl-L-alanine.
[7]根据[1]-[6]任一项所述的凝胶组合物,所述碱性氨基酸选自精氨酸、赖氨酸、瓜氨酸、鸟氨酸、肌酸、组氨酸、二氨基丁酸、二氨基丙酸中的一种或多种,优选精氨酸和/或赖氨酸,最优选精氨酸;[7] The gel composition according to any one of [1] to [6], wherein the basic amino acid is selected from one or more of arginine, lysine, citrulline, ornithine, creatine, histidine, diaminobutyric acid, and diaminopropionic acid, preferably arginine and/or lysine, most preferably arginine;
和/或,所述无机碱选自氢氧化钠、氢氧化钾中的一种或多种,优选氢氧化钠。And/or, the inorganic base is selected from one or more of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide.
[8]根据[1]-[7]任一项所述的凝胶组合物,所述N-长链酰基氨基酸二肽中的N-长链酰基来源于碳原子数8~22的饱和或不饱和直链或支链的脂肪酸;优选的,所述N-长链酰基氨基酸二肽中的N-长链酰基选自辛酰基、癸酰基、十一烷酰基、月桂酰基、肉豆蔻酰基、十五烷酰基、棕榈酰基、硬脂酰基、油酰基、亚油酰基、异硬脂酰基、椰子油脂肪酰基、棕榈油脂肪酰基中的一种或多种,优选椰子油脂肪酰基或月桂酰基,最优选月桂酰基;[8] The gel composition according to any one of [1] to [7], wherein the N-long-chain acyl group in the N-long-chain acyl amino acid dipeptide is derived from a saturated or unsaturated straight-chain or branched fatty acid having 8 to 22 carbon atoms; preferably, the N-long-chain acyl group in the N-long-chain acyl amino acid dipeptide is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
和/或,所述N-长链酰基氨基酸二肽中的氨基酸来源于丙氨酸、甘氨酸、谷氨酸、肌氨酸、精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种,优选L-丙氨酸。And/or, the amino acid in the N-long-chain acyl amino acid dipeptide is derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably L-alanine.
[9]根据[1]-[8]任一项所述的凝胶组合物,所述N-长链酰基氨基酸二肽选自长链酰基甘氨酰甘氨酸、长链酰基谷氨酰谷氨酸、长链酰基丙氨酰丙氨酸、长链酰基肌氨酰肌氨酸中的一种或多种。[9] According to the gel composition according to any one of [1] to [8], the N-long-chain acyl amino acid dipeptide is selected from one or more of long-chain acyl glycylglycine, long-chain acyl glutamyl glutamate, long-chain acyl alanyl alanine, and long-chain acyl sarcosyl sarcosine.
[10]根据[2],[4]-[9]任一项任一项所述的凝胶组合物,N-长链酰基氨基酸重量百分含量在55wt%以下,优选在50wt%以下,更优选在45wt%以下。[10] The gel composition according to any one of [2], [4] to [9], wherein the weight percentage of N-long-chain acylamino acid is less than 55 wt%, preferably less than 50 wt%, and more preferably less than 45 wt%.
[11]根据[3]-[9]任一项所述的凝胶组合物,N-长链酰基氨基酸重 量百分含量在75wt%以下,优选在65wt%以下,更优选在60wt%以下。[11] The gel composition according to any one of [3] to [9], wherein the N-long-chain acylamino acid is The content percentage is below 75wt%, preferably below 65wt%, and more preferably below 60wt%.
[12]根据权利要求[1]-[11]任一项所述的凝胶组合物,N-长链酰基氨基酸二肽重量百分含量在0.5wt%以上,优选在0.75wt%以上,更优选在1wt%以上;[12] The gel composition according to any one of claims [1] to [11], wherein the weight percentage of the N-long-chain acylamino acid dipeptide is greater than 0.5 wt%, preferably greater than 0.75 wt%, and more preferably greater than 1 wt%;
和/或,N-长链酰基氨基酸与N-长链酰基氨基酸二肽重量比为20:1至1.5:1,优选15:1至3:1,更优选10:1至6:1。And/or, the weight ratio of N-long-chain acyl amino acid to N-long-chain acyl amino acid dipeptide is 20:1 to 1.5:1, preferably 15:1 to 3:1, more preferably 10:1 to 6:1.
[13]根据[1]-[12]任一项所述的凝胶组合物,所述碱性氨基酸或无机碱以足以部分或完全中和N-长链酰基氨基酸、N-长链酰基氨基酸二肽的量存在,优选中和度在85%以上,更优选中和度在88%或90%以上,且小于100%;优选的,中和度为85%-98%,88%-96%,更优选90%-95%。[13] According to the gel composition described in any one of [1] to [12], the basic amino acid or inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acyl amino acid or N-long-chain acyl amino acid dipeptide, preferably with a neutralization degree of 85% or more, more preferably with a neutralization degree of 88% or 90% or more, and less than 100%; preferably, the neutralization degree is 85%-98%, 88%-96%, more preferably 90%-95%.
[14]根据[1]-[13]任一项所述的凝胶组合物,组合物中不含或基本不含增稠剂,优选完全不含增稠剂;[14] The gel composition according to any one of [1] to [13], wherein the composition contains no or substantially no thickener, and preferably contains no thickener at all;
和/或,组合物中不含或基本不含氯化钠。And/or, the composition is free or substantially free of sodium chloride.
[15]根据[14]所述的凝胶组合物,所述增稠剂选自纤维素类、粘多糖类、聚乙烯醇类、胶质类、聚丙烯酸钠类、聚乙烯基吡咯烷酮类、乙烯基聚合物类中的一种或多种。[15] According to the gel composition described in [14], the thickener is selected from one or more of cellulose, mucopolysaccharides, polyvinyl alcohols, colloids, sodium polyacrylates, polyvinyl pyrrolidones, and vinyl polymers.
[16]根据[1]-[15]任一项所述的凝胶组合物,按GB/T 13531.1中规定的稀释法,测凝胶组合物的pH值,pH值在4.5以上,优选5以上,更优选5.5以上;且pH值在12以下,优选11以下,更优选10以下。[16] According to any one of items [1] to [15], the pH value of the gel composition is measured by the dilution method specified in GB/T 13531.1, and the pH value is above 4.5, preferably above 5, and more preferably above 5.5; and the pH value is below 12, preferably below 11, and more preferably below 10.
[17]根据[1]-[16]任一项所述的凝胶组合物,组合物形成凝胶后,利用日本RHEOTECH硬度计检测,在荷重2kg、适配器20mmφ、针入速度6cm/min、针入距离10mm的检测条件下,硬度在1.80以下,优选在1.50以下,更优选在1.00以下。[17] The gel composition according to any one of [1] to [16], after the composition forms a gel, is tested using a Japanese RHEOTECH hardness tester under the test conditions of a load of 2 kg, an adapter of 20 mmφ, a needle penetration speed of 6 cm/min, and a needle penetration distance of 10 mm. The hardness is below 1.80, preferably below 1.50, and more preferably below 1.00.
[18]根据[1]-[17]任一项所述的凝胶组合物,组合物进一步包含水溶性油脂和/或烷基糖苷。[18] The gel composition according to any one of [1] to [17], further comprising a water-soluble oil and/or an alkyl glycoside.
[19]根据[18]所述的凝胶组合物,所述水溶性油脂选自PEG橄榄油酯类、PEG异硬脂酸酯类、PEG椰油基酯类、PEG鳄梨酯类中的 一种或多种;优选PEG-10橄榄油甘油酯类、橄榄油PEG-7酯类、橄榄油PEG-8酯类、PEG-7橄榄油酸酯、PEG-15甘油异硬脂酸酯、PEG-9椰油基甘油酯类、PEG-11鳄梨甘油酯类中的一种或多种。[19] The gel composition according to [18], wherein the water-soluble oil is selected from PEG olive oil esters, PEG isostearates, PEG coconut oil esters, PEG avocado esters. One or more; preferably one or more of PEG-10 olive oil glycerides, olive oil PEG-7 esters, olive oil PEG-8 esters, PEG-7 olive oil esters, PEG-15 glyceryl isostearate, PEG-9 coconut oil glycerides, and PEG-11 avocado glycerides.
[20]一种凝胶,其基于N-长链酰基氨基酸、碱性氨基酸的自增稠形成;[20] A gel formed by self-thickening of N-long-chain acylamino acids and basic amino acids;
或者,基于N-长链酰基氨基酸、碱性氨基酸、N-长链酰基氨基酸二肽的自增稠形成凝胶;Alternatively, the self-thickening gel is formed based on N-long-chain acyl amino acids, basic amino acids, and N-long-chain acyl amino acid dipeptides;
或者,基于N-长链酰基氨基酸、无机碱的自增稠形成凝胶;Alternatively, the gel is formed based on the self-thickening of N-long-chain acylamino acids and inorganic bases;
或者,基于N-长链酰基氨基酸、无机碱、N-长链酰基氨基酸二肽的自增稠形成凝胶。Alternatively, the self-thickening gel is formed based on N-long chain acyl amino acids, inorganic bases, and N-long chain acyl amino acid dipeptides.
[21]一种凝胶,由[1]-[19]任一项所述的凝胶组合物制备得到。[21] A gel prepared from the gel composition described in any one of [1] to [19].
[22]根据[20]或[21]所述的凝胶,凝胶在40±1℃保持24h,恢复室温后可正常使用;[22] The gel according to [20] or [21], wherein the gel is kept at 40±1°C for 24 hours and can be used normally after returning to room temperature;
和/或,凝胶在-8±2℃保持24h,恢复室温后可正常使用。And/or, the gel is kept at -8±2°C for 24 hours and can be used normally after returning to room temperature.
[23]根据[20]-[22]任一项所述的凝胶,所述凝胶为清洁凝胶、护肤凝胶、洗发凝胶、沐浴凝胶、剃须凝胶、卸妆凝胶、按摩凝胶、化妆用凝胶、口腔用凝胶或多功能凝胶。[23] The gel according to any one of [20] to [22], which is a cleansing gel, a skin care gel, a shampoo gel, a shower gel, a shaving gel, a makeup remover gel, a massage gel, a cosmetic gel, an oral gel or a multi-purpose gel.
[24]一种[1]-[19]任一项所述的凝胶组合物的用途,用于清洁组合物、洗涤组合物、化妆品组合物、皮肤护理组合物或口腔护理组合物。[24] Use of the gel composition described in any one of [1] to [19] in a cleaning composition, a detergent composition, a cosmetic composition, a skin care composition or an oral care composition.
[25]一种牙膏,含有[1]-[19]任一项所述的凝胶组合物。[25] A toothpaste comprising the gel composition described in any one of [1] to [19].
[26]一种化妆品,含有[1]-[19]任一项所述的凝胶组合物。[26] A cosmetic comprising the gel composition described in any one of [1] to [19].
[27]一种清洁产品,含有[1]-[19]任一项所述的凝胶组合物。[27] A cleaning product comprising the gel composition described in any one of [1] to [19].
[28]一种[1]-[19]任一项所述的凝胶组合物的制备方法,包含如下步骤:[28] A method for preparing the gel composition according to any one of [1] to [19], comprising the following steps:
在75-90℃,优选80-85℃条件下,混合(a)、(b)或(e)、(c)和任选的(d);Mixing (a), (b) or (e), (c) and optionally (d) at 75-90°C, preferably 80-85°C;
优选的,先将(b)或(e)与(c)混合得到溶液I,之后在75-90℃、优 选80-85℃条件下使得(a)和任选的(d)熔融得到溶液II,最后,在75-90℃、优选80-85℃条件下,将溶液I与溶液II混合。Preferably, (b) or (e) is first mixed with (c) to obtain solution I, and then heated at 75-90°C, preferably (a) and optionally (d) are melted at 80-85°C to obtain solution II. Finally, solution I is mixed with solution II at 75-90°C, preferably 80-85°C.
[29]一种赋予清洁组合物凝胶特性的方法,清洁组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上,碱性氨基酸重量百分含量在15wt%以上,优选17wt%以上,更优选20wt%以上;[29] A method for imparting gel properties to a cleaning composition, the cleaning composition comprising (a) an N-long-chain acyl amino acid, and (b) a basic amino acid, wherein the weight percentage of the N-long-chain acyl amino acid is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the basic amino acid is greater than 15 wt %, preferably greater than 17 wt %, more preferably greater than 20 wt %;
或者,清洁组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在20wt%以上,优选23wt%以上,更优选25wt%以上,碱性氨基酸重量百分含量在10wt%以上,优选12wt%以上,更优选14wt%以上;Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid, (b) a basic amino acid, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 20 wt %, preferably greater than 23 wt %, more preferably greater than 25 wt %, and the weight percentage of the basic amino acid is greater than 10 wt %, preferably greater than 12 wt %, more preferably greater than 14 wt %;
或者,清洁组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,其中,N-长链酰基氨基酸重量百分含量在20wt%以上,优选23wt%以上,更优选25wt%以上,N-长链酰基氨基酸与碱性氨基酸的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid and (b) a basic amino acid, wherein the weight percentage of the N-long-chain acyl amino acid is above 20 wt %, preferably above 23 wt %, more preferably above 25 wt %, and the molar ratio of the N-long-chain acyl amino acid to the basic amino acid is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
[30]一种赋予清洁组合物凝胶特性的方法,清洁组合物包含(a)N-长链酰基氨基酸,(e)无机碱,其中,N-长链酰基氨基酸重量百分含量在40wt%以上,优选43wt%以上,更优选45wt%以上,无机碱重量百分含量在5.5wt%以上,优选6wt%以上,更优选6.5wt%以上;[30] A method for imparting gel properties to a cleaning composition, the cleaning composition comprising (a) an N-long-chain acylamino acid, and (e) an inorganic base, wherein the weight percentage of the N-long-chain acylamino acid is greater than 40 wt %, preferably greater than 43 wt %, more preferably greater than 45 wt %, and the weight percentage of the inorganic base is greater than 5.5 wt %, preferably greater than 6 wt %, more preferably greater than 6.5 wt %;
或者,清洁组合物包含(a)N-长链酰基氨基酸,(e)无机碱,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在30wt%以上,优选33wt%以上,更优选35wt%以上,无机碱重量百分含量在4wt%以上,优选4.5wt%以上,更优选5wt%以上;Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the inorganic base is greater than 4 wt %, preferably greater than 4.5 wt %, more preferably greater than 5 wt %;
或者,清洁组合物包含(a)N-长链酰基氨基酸,(e)无机碱,其中,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上,N-长链酰基氨基酸与无机碱的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid and (e) an inorganic base, wherein the weight percentage of the N-long-chain acyl amino acid is above 30 wt %, preferably above 33 wt %, more preferably above 35 wt %, and the molar ratio of the N-long-chain acyl amino acid to the inorganic base is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
[31]根据[29]或[30]所述的方法,所述N-长链酰基氨基酸中的N-长链酰基选自辛酰基、癸酰基、十一烷酰基、月桂酰基、肉豆蔻酰基、十五烷酰基、棕榈酰基、硬脂酰基、油酰基、亚油酰基、异硬 脂酰基、椰子油脂肪酰基、棕榈油脂肪酰基中的一种或多种,优选椰子油脂肪酰基或月桂酰基,最优选月桂酰基;[31] The method according to [29] or [30], wherein the N-long-chain acyl group in the N-long-chain acyl amino acid is selected from octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearyl, styroyl, styroyl, linoleyl, styro ... One or more of fatty acyl, coconut oil fatty acyl, palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, most preferably lauroyl;
和/或,所述N-长链酰基氨基酸中的氨基酸来源于丙氨酸、甘氨酸、谷氨酸、肌氨酸、精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种,优选丙氨酸,最优选L-丙氨酸。And/or, the amino acid in the N-long-chain acylamino acid is derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
[32]根据[29]-[31]任一项所述的方法,所述碱性氨基酸选自精氨酸、赖氨酸、瓜氨酸、鸟氨酸、肌酸、组氨酸、二氨基丁酸、二氨基丙酸中的一种或多种,优选精氨酸和/或赖氨酸,最优选精氨酸;[32] The method according to any one of [29] to [31], wherein the basic amino acid is selected from one or more of arginine, lysine, citrulline, ornithine, creatine, histidine, diaminobutyric acid, and diaminopropionic acid, preferably arginine and/or lysine, most preferably arginine;
和/或,所述无机碱选自氢氧化钠、氢氧化钾中的一种或多种,优选氢氧化钠。And/or, the inorganic base is selected from one or more of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide.
[33]根据[29]-[32]任一项所述的方法,所述N-长链酰基氨基酸二肽中的N-长链酰基选自辛酰基、癸酰基、十一烷酰基、月桂酰基、肉豆蔻酰基、十五烷酰基、棕榈酰基、硬脂酰基、油酰基、亚油酰基、异硬脂酰基、椰子油脂肪酰基、棕榈油脂肪酰基中的一种或多种,优选椰子油脂肪酰基或月桂酰基,最优选月桂酰基;[33] The method according to any one of [29] to [32], wherein the N-long-chain acyl group in the N-long-chain acyl amino acid dipeptide is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
和/或,所述N-长链酰基氨基酸二肽中的氨基酸来源于丙氨酸、甘氨酸、谷氨酸、肌氨酸、精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种,优选丙氨酸,最优选L-丙氨酸。And/or, the amino acids in the N-long-chain acyl amino acid dipeptide are derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
优选的,所述N-长链酰基氨基酸二肽选自长链酰基甘氨酰甘氨酸、长链酰基谷氨酰谷氨酸、长链酰基丙氨酰丙氨酸、长链酰基肌氨酰肌氨酸中的一种或多种。Preferably, the N-long-chain acyl amino acid dipeptide is selected from one or more of long-chain acyl glycylglycine, long-chain acyl glutamyl glutamate, long-chain acyl alanyl alanine, and long-chain acyl sarcosyl sarcosine.
[34]根据[29]所述的方法,N-长链酰基氨基酸重量百分含量在55wt%以下,优选在50wt%以下,更优选在45wt%以下。[34] According to the method described in [29], the weight percentage of N-long-chain acyl amino acid is less than 55wt%, preferably less than 50wt%, and more preferably less than 45wt%.
[35]根据[30]所述的方法,N-长链酰基氨基酸重量百分含量在75wt%以下,优选在65wt%以下,更优选在60wt%以下。[35] According to the method described in [30], the weight percentage of N-long-chain acyl amino acid is less than 75wt%, preferably less than 65wt%, and more preferably less than 60wt%.
[36]根据[29]-[35]任一项所述的方法,N-长链酰基氨基酸二肽重量百分含量在0.5wt%以上,优选在0.75wt%以上,更优选在1wt%以上;和/或,N-长链酰基氨基酸与N-长链酰基氨基酸二肽重量比为20:1至1.5:1,优选15:1至3:1,更优选10:1至6:1。[36] The method according to any one of [29] to [35], wherein the weight percentage of the N-long-chain acyl amino acid dipeptide is greater than 0.5 wt%, preferably greater than 0.75 wt%, more preferably greater than 1 wt%; and/or the weight ratio of the N-long-chain acyl amino acid to the N-long-chain acyl amino acid dipeptide is from 20:1 to 1.5:1, preferably from 15:1 to 3:1, more preferably from 10:1 to 6:1.
[37]根据[29]-[36]任一项所述的方法,组合物中不含或基本不含 增稠剂;和/或,组合物中不含或基本不含氯化钠。[37] The method according to any one of [29] to [36], wherein the composition does not contain or substantially does not contain and/or, the composition contains no or substantially no sodium chloride.
[38]根据[29]-[37]任一项所述的方法,所述碱性氨基酸或无机碱以足以部分或完全中和N-长链酰基氨基酸、N-长链酰基氨基酸二肽的量存在,优选中和度在85%以上,更优选中和度在88%以上,且小于100%。[38] According to the method described in any one of [29] to [37], the basic amino acid or inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acyl amino acid or N-long-chain acyl amino acid dipeptide, and the degree of neutralization is preferably above 85%, more preferably above 88% and less than 100%.
[39]根据前述任一项所述,组合物由(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水和任选的(d)N-长链酰基氨基酸二肽组成;或者,组合物由(a)N-长链酰基氨基酸,(e)无机碱,(c)水和任选的(d)N-长链酰基氨基酸二肽组成;或者,由(a)N-长链酰基氨基酸,(b)碱性氨基酸/(e)无机碱,(c)水和任选的(d)N-长链酰基氨基酸二肽,防腐剂和/或甜味剂组成。[39] According to any of the preceding items, the composition consists of (a) N-long-chain acyl amino acid, (b) basic amino acid, (c) water and optionally (d) N-long-chain acyl amino acid dipeptide; or, the composition consists of (a) N-long-chain acyl amino acid, (e) inorganic base, (c) water and optionally (d) N-long-chain acyl amino acid dipeptide; or, the composition consists of (a) N-long-chain acyl amino acid, (b) basic amino acid/(e) inorganic base, (c) water and optionally (d) N-long-chain acyl amino acid dipeptide, a preservative and/or a sweetener.
与现有技术相比,本发明具有有益的技术效果:Compared with the prior art, the present invention has the following beneficial technical effects:
1.本发明的凝胶组合物/凝胶产品以氨基酸表面活性剂((a)成分)作为主表面活性剂/唯一表面活性剂,尤其是在与碱性氨基酸((b)成分)复配时,产品绿色、环保,无毒无害,在使用过程中对人体皮肤非常温和,无刺激,并可减少对石油基产品的依赖。1. The gel composition/gel product of the present invention uses an amino acid surfactant (component (a)) as the main surfactant/only surfactant, especially when compounded with a basic amino acid (component (b)). The product is green, environmentally friendly, non-toxic and harmless, is very gentle and non-irritating to human skin during use, and can reduce dependence on petroleum-based products.
2.本发明在不使用传统增稠剂/凝胶化剂的情况下,制备出凝胶产品,避免了增稠剂/凝胶化剂对产品性能(颜色、泡沫、功效、使用感受等)的影响。2. The present invention prepares a gel product without using a traditional thickener/gelling agent, thereby avoiding the influence of the thickener/gelling agent on product performance (color, foam, efficacy, use experience, etc.).
3.出人意料的发现,N-长链酰基氨基酸二肽的加入,能够大大降低原料使用量(即,使用更少量的N-长链酰基氨基酸即可形成凝胶),也能够一定程度提升凝胶的耐热和耐寒性能,提升凝胶的挤出和截断性能。3. It was unexpectedly found that the addition of N-long-chain acyl amino acid dipeptide can greatly reduce the amount of raw materials used (i.e., a smaller amount of N-long-chain acyl amino acid can be used to form a gel), and can also improve the heat and cold resistance of the gel to a certain extent, and improve the extrusion and truncation performance of the gel.
4.出人意料的发现,中和度在85%以上且小于100%时(即,N-长链酰基氨基酸/二肽未被完全中和,体系内含有少量N-长链酰基氨基酸/二肽),能够大大降低原料使用量,凝胶更软,提升凝胶的挤出和截断性能。4. It was unexpectedly found that when the degree of neutralization is above 85% and less than 100% (i.e., the N-long-chain acyl amino acid/dipeptide is not completely neutralized and the system contains a small amount of N-long-chain acyl amino acid/dipeptide), the amount of raw materials used can be greatly reduced, the gel is softer, and the extrusion and cutting properties of the gel are improved.
5.凝胶态的清洁产品携带方便,非常适用于户外、商超等各种非居家场景。 5. Gel-state cleaning products are easy to carry and are very suitable for various non-home scenarios such as outdoors and supermarkets.
6.复配(a)N-长链酰基氨基酸、(b)碱性氨基酸以及任选的(d)N-长链酰基氨基酸二肽形成的凝胶具有多功能性,有非常好的清洁力,可以作为洗手产品、沐浴产品、洗发产品、卸妆产品使用,也可以作为牙膏使用;在户外,可以作为野外餐具等的清洁剂使用。6. The gel formed by compounding (a) N-long-chain acyl amino acid, (b) basic amino acid and optionally (d) N-long-chain acyl amino acid dipeptide is multifunctional and has very good cleaning power. It can be used as a hand washing product, bath product, shampoo product, makeup remover product, and can also be used as toothpaste. Outdoors, it can be used as a cleaning agent for outdoor tableware, etc.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1-7的凝胶外观,其中,a~g依次为实施例1~7凝胶的外观;FIG1 is the appearance of the gels of Examples 1-7, wherein a to g are the appearance of the gels of Examples 1 to 7, respectively;
图2为实施例8-10的凝胶外观,其中,a~c依次为实施例8~10凝胶的外观(a为实施例8凝胶外观,b为实施例9凝胶外观,c为实施例10凝胶外观);FIG2 is the appearance of the gels of Examples 8-10, wherein a to c are the appearance of the gels of Examples 8 to 10 respectively (a is the appearance of the gel of Example 8, b is the appearance of the gel of Example 9, and c is the appearance of the gel of Example 10);
图3为实施例11-12的凝胶外观,其中,a为实施例11凝胶外观,b为实施例12凝胶外观;FIG3 is the appearance of the gel of Example 11-12, wherein a is the appearance of the gel of Example 11, and b is the appearance of the gel of Example 12;
图4为实施例13-15的凝胶外观,其中,a~c依次为实施例13~15凝胶的外观;FIG4 is the appearance of the gels of Examples 13-15, wherein a to c are the appearance of the gels of Examples 13 to 15, respectively;
图5为实施例16的凝胶外观。FIG5 shows the appearance of the gel of Example 16.
具体实施方式Detailed ways
在一个实施方式中,提供一种凝胶组合物。该组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水。In one embodiment, a gel composition is provided, comprising (a) N-long-chain acylamino acid, (b) basic amino acid, and (c) water.
对于组分(a),N-长链酰基氨基酸中的N-长链酰基来源于碳原子数8~22的饱和或不饱和直链或支链的脂肪酸。进一步的,所述N-长链酰基氨基酸中的N-长链酰基选自辛酰基、癸酰基、十一烷酰基、月桂酰基、肉豆蔻酰基、十五烷酰基、棕榈酰基、硬脂酰基、油酰基、亚油酰基、异硬脂酰基、椰子油脂肪酰基、棕榈油脂肪酰基中的一种或多种,优选椰子油脂肪酰基或月桂酰基,最优选月桂酰基。For component (a), the N-long-chain acyl group in the N-long-chain acyl amino acid is derived from a saturated or unsaturated straight-chain or branched fatty acid having 8 to 22 carbon atoms. Further, the N-long-chain acyl group in the N-long-chain acyl amino acid is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl.
N-长链酰基氨基酸中的氨基酸来源于甘氨酸、丙氨酸、谷氨酸、肌氨酸、天冬氨酸、亮氨酸、异亮氨酸、缬氨酸、苏氨酸、脯氨酸、苯丙氨酸、精氨酸、赖氨酸中的一种或多种。进一步的,所述N-长链酰基氨基酸中的氨基酸来源于丙氨酸、甘氨酸、谷氨酸、肌氨酸、 精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种,优选丙氨酸,最优选L-丙氨酸。The amino acids in the N-long chain acyl amino acids are derived from one or more of glycine, alanine, glutamic acid, sarcosine, aspartic acid, leucine, isoleucine, valine, threonine, proline, phenylalanine, arginine, and lysine. Further, the amino acids in the N-long chain acyl amino acids are derived from one or more of alanine, glycine, glutamic acid, sarcosine, One or more of arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
本文所述N-长链酰基(甲基)牛磺酸是指N-长链酰基甲基牛磺酸或N-长链酰基牛磺酸。The N-long-chain acyl (methyl) taurine mentioned herein refers to N-long-chain acyl methyl taurine or N-long-chain acyl taurine.
作为实例,N-长链酰基氨基酸可选自椰油酰基丙氨酸、月桂酰基丙氨酸、椰油酰基肌氨酸、月桂酰肌氨酸、月桂酰谷氨酸、椰油酰谷氨酸、油酰谷氨酸、椰油酰甘氨酸、月桂酰甘氨酸、硬脂酰谷氨酸等,优选月桂酰基丙氨酸、月桂酰肌氨酸,尤其优选N-月桂酰-L-丙氨酸。也可以选择相关N-长链酰基氨基酸的盐作为起始原料,本领域技术人员能够理解,其与相应酸作为起始原料,并无本质区别,属于等同技术特征。As an example, the N-long-chain acyl amino acid can be selected from cocoyl alanine, lauroyl alanine, cocoyl sarcosine, lauroyl sarcosine, lauroyl glutamic acid, cocoyl glutamic acid, oleoyl glutamic acid, cocoyl glycine, lauroyl glycine, stearoyl glutamic acid, etc., preferably lauroyl alanine, lauroyl sarcosine, especially preferably N-lauroyl-L-alanine. Salts of the relevant N-long-chain acyl amino acids can also be selected as starting materials, and those skilled in the art will understand that there is no essential difference between them and the corresponding acids as starting materials, and they belong to equivalent technical features.
N-长链酰基氨基酸的合成工艺,可以参照N-酰基氨基酸型表面活性剂的一般合成方法,分为直接法和间接法。脂肪酸原料直接合成法包括酶催化合成和脱水缩合。间接合成法有脂肪酰氯酰化、脂肪腈水解酰化、脂肪酸酐酰化、酰胺羰基化反应等。较为优选的,是通过脂肪酰氯与氨基酸的氨基反应(Shotten-Baumann缩合反应或肖顿-鲍曼反应)来制备。The synthesis process of N-long-chain acylamino acids can refer to the general synthesis method of N-acylamino acid type surfactants, which can be divided into direct method and indirect method. The direct synthesis method of fatty acid raw materials includes enzyme catalytic synthesis and dehydration condensation. The indirect synthesis method includes fatty acid chloride acylation, fatty nitrile hydrolysis acylation, fatty acid anhydride acylation, amide carbonylation reaction, etc. More preferably, it is prepared by the reaction of fatty acid chloride with the amino group of amino acid (Shotten-Baumann condensation reaction or Shotten-Baumann reaction).
适合本发明的典型制备过程如:氨基酸和氢氧化钠溶于水或水和丙酮的混合溶液中得到氨基酸盐溶液;之后向氨基酸盐溶液中缓慢滴加月桂酰氯、氢氧化钠溶液,控制反应体系的pH,滴加完毕后,进行产物的后处理。代表性的方法公开于CN1798821A、US6703517B2、CN102875409B、JPH0570418A等。A typical preparation process suitable for the present invention is as follows: amino acid and sodium hydroxide are dissolved in water or a mixed solution of water and acetone to obtain an amino acid salt solution; then lauroyl chloride and sodium hydroxide solution are slowly added dropwise to the amino acid salt solution to control the pH of the reaction system, and after the addition is completed, the product is post-treated. Representative methods are disclosed in CN1798821A, US6703517B2, CN102875409B, JPH0570418A, etc.
对于N-长链酰基氨基酸产物的后处理,可以使用常规的重结晶、水洗涤、干燥等。优选后处理包含如下步骤:将N-长链酰基氨基酸粗品与溶剂混合,任选搅拌,控制混合后体系的温度T在长链脂肪酸熔点以上且在N-长链酰基氨基酸熔点以下,所述溶剂为水或有机溶剂或水与有机溶剂的混合溶液;体系控温后,进行固液分离操作。相关方法被本发明人公开于CN202210867760.7、PCT/CN2022/107270,在此,将相关内容一并引入。For the post-treatment of the N-long-chain acyl amino acid product, conventional recrystallization, water washing, drying, etc. can be used. Preferably, the post-treatment comprises the following steps: mixing the crude N-long-chain acyl amino acid with a solvent, optionally stirring, and controlling the temperature T of the mixed system to be above the melting point of the long-chain fatty acid and below the melting point of the N-long-chain acyl amino acid, wherein the solvent is water or an organic solvent or a mixed solution of water and an organic solvent; after the system is temperature controlled, a solid-liquid separation operation is performed. The relevant methods are disclosed by the inventors in CN202210867760.7 and PCT/CN2022/107270, and the relevant contents are introduced here.
对于组分(b),碱性氨基酸选自精氨酸、赖氨酸、瓜氨酸、鸟氨酸、肌酸、组氨酸、二氨基丁酸、二氨基丙酸中的一种或多种,优 选精氨酸和/或赖氨酸,最优选精氨酸。一方面,精氨酸有利于凝胶产品的耐热性和耐寒性,且凝胶适宜挤出;另一方面,在口腔凝胶方面,精氨酸具有促进钙磷离子沉积于牙本质表面和牙本质小管的能力,同时具有隔绝外界刺激、延缓牙本质敏感的作用。For component (b), the basic amino acid is selected from one or more of arginine, lysine, citrulline, ornithine, creatine, histidine, diaminobutyric acid, and diaminopropionic acid, preferably Arginine and/or lysine are selected, and arginine is most preferred. On the one hand, arginine is beneficial to the heat resistance and cold resistance of the gel product, and the gel is suitable for extrusion; on the other hand, in terms of oral gel, arginine has the ability to promote the deposition of calcium and phosphorus ions on the dentin surface and dentinal tubules, and at the same time has the effect of isolating external stimulation and delaying dentin sensitivity.
对于上述组分(a)和(b),也可以直接添加N-长链酰基氨基酸的碱性氨基酸盐,其与分别添加组分(a)和(b)并无本质区别,也涵盖在本发明保护的范围内。For the above components (a) and (b), the basic amino acid salt of N-long-chain acyl amino acid can also be directly added, which is not essentially different from adding components (a) and (b) separately, and is also covered by the scope of protection of the present invention.
对于组分(c),没有特别限定。具体地,可以使用离子交换水,蒸馏水、纯净水、河水、井水,天然水,地下水,城市水,硬水,软水等。可以使用这些中的一种,或者可以混合使用从上述组中选择的两种以上。从本发明产品的储存稳定性和卫生的观点出发,优选离子交换水、蒸馏水、纯净水。Component (c) is not particularly limited. Specifically, ion exchange water, distilled water, purified water, river water, well water, natural water, groundwater, city water, hard water, soft water, etc. can be used. One of these can be used, or two or more selected from the above group can be mixed and used. From the viewpoint of storage stability and sanitation of the product of the present invention, ion exchange water, distilled water, purified water are preferred.
本实施方式中使用的组分(a)N-长链酰基氨基酸重量百分含量在30wt%以上,优选31wt%、32wt%、33wt%、34wt%、35wt%以上,如果用量过低,则难以获得凝胶。如无特殊说明,本发明中的重量百分含量均相对于组合物而言。The weight percentage of component (a) N-long-chain acylamino acid used in this embodiment is above 30wt%, preferably above 31wt%, 32wt%, 33wt%, 34wt%, 35wt%. If the amount is too low, it is difficult to obtain a gel. Unless otherwise specified, the weight percentages in the present invention are relative to the composition.
组分(a)N-长链酰基氨基酸重量百分含量在55wt%以下,优选54wt%、53wt%、52wt%、51wt%、50wt%、49wt%、48wt%、47wt%、46wt%、45wt%、44wt%、43wt%、42wt%、41wt%、40wt%以下,如果用量过高,则凝胶偏硬,不利于挤出和截断。The weight percentage of component (a) N-long-chain acylamino acid is below 55wt%, preferably 54wt%, 53wt%, 52wt%, 51wt%, 50wt%, 49wt%, 48wt%, 47wt%, 46wt%, 45wt%, 44wt%, 43wt%, 42wt%, 41wt%, 40wt% or less. If the dosage is too high, the gel will be too hard, which is not conducive to extrusion and cutting.
组分(b)碱性氨基酸重量百分含量在15wt%以上,优选16wt%、17wt%、18wt%、19wt%、20wt%、21wt%、22wt%以上。The weight percentage of the basic amino acid in component (b) is above 15wt%, preferably above 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%.
在一个实施方式中,提供一种凝胶组合物。该组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,其中,N-长链酰基氨基酸重量百分含量在20wt%以上,优选23wt%以上,更优选25wt%以上。组分(a)、(b)、(c)参见其他实施方式中的相关描述。In one embodiment, a gel composition is provided. The composition comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, and (c) water, wherein the weight percentage of N-long-chain acyl amino acid is above 20wt%, preferably above 23wt%, and more preferably above 25wt%. Components (a), (b), and (c) refer to the relevant descriptions in other embodiments.
优选的,碱性氨基酸以足以部分或完全中和N-长链酰基氨基酸的量存在。在一优选方案中,中和度在85%以上,更优选中和度在88%以上。例如中和度为86%、87%、88%、89%、90%、91%、92%、93%、94%、95%、96%、97%、98%。 Preferably, the basic amino acid is present in an amount sufficient to partially or completely neutralize the N-long-chain acylamino acid. In a preferred embodiment, the degree of neutralization is above 85%, more preferably above 88%. For example, the degree of neutralization is 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%.
进一步的,从摩尔比的角度,N-长链酰基氨基酸与碱性氨基酸的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。示例性的,当N-长链酰基氨基酸为1mol时,碱性氨基酸为0.98、0.97、0.96、0.95、0.94、0.93、0.92、0.91、0.90、0.89、0.88、0.87、0.86或0.85mol。Further, from the perspective of molar ratio, the molar ratio of N-long chain acyl amino acid to basic amino acid is 1: 0.98 to 1: 0.85, preferably 1: 0.96 to 1: 0.88, more preferably 1: 0.95 to 1: 0.90. Exemplarily, when the N-long chain acyl amino acid is 1 mol, the basic amino acid is 0.98, 0.97, 0.96, 0.95, 0.94, 0.93, 0.92, 0.91, 0.90, 0.89, 0.88, 0.87, 0.86 or 0.85 mol.
本发明出人意料的发现,中和度在85%以上且小于100%时,组合物体系内含有少量未中和的N-长链酰基氨基酸和/或N-长链酰基氨基酸二肽,能够大大降低原料使用量,使得凝胶更软,提升凝胶的挤出和截断性能。但是如果N-长链酰基氨基酸和/或N-长链酰基氨基酸二肽残留过多,则对体系稳定性有不利影响,过多的N-长链酰基氨基酸可能在产品使用过程中逐渐析出或者出现泛白现象。The present invention surprisingly found that when the degree of neutralization is above 85% and less than 100%, a small amount of unneutralized N-long-chain acyl amino acids and/or N-long-chain acyl amino acid dipeptides are contained in the composition system, which can greatly reduce the amount of raw materials used, make the gel softer, and improve the extrusion and truncation performance of the gel. However, if too much N-long-chain acyl amino acids and/or N-long-chain acyl amino acid dipeptides remain, it will have an adverse effect on the stability of the system, and too much N-long-chain acyl amino acids may gradually precipitate or appear whitening during the use of the product.
在一个实施方式中,提供一种凝胶组合物。该组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,(d)N-长链酰基氨基酸二肽。In one embodiment, a gel composition is provided, which comprises (a) an N-long-chain acyl amino acid, (b) a basic amino acid, (c) water, and (d) an N-long-chain acyl amino acid dipeptide.
组分(a)、(b)、(c)参见其他实施方式中的相关描述,在此,不再赘述。组分(d)N-长链酰基氨基酸二肽是已知概念,长链酰基氨基酸二肽是指长链酰基氨基酰基氨基酸,典型的如长链酰基甘氨酰甘氨酸、长链酰基谷氨酰谷氨酸、长链酰基丙氨酰丙氨酸、长链酰基肌氨酰肌氨酸等,例如参见CN100448968C、PCT/CN2022/107270等。Components (a), (b), and (c) refer to the relevant descriptions in other embodiments, and are not repeated here. Component (d) N-long-chain acyl amino acid dipeptide is a known concept, and long-chain acyl amino acid dipeptide refers to long-chain acylaminoacyl amino acids, typically long-chain acyl glycyl glycine, long-chain acyl glutamyl glutamic acid, long-chain acyl alanyl alanine, long-chain acyl sarcosyl sarcosine, etc., for example, see CN100448968C, PCT/CN2022/107270, etc.
N-长链酰基氨基酸二肽可以由N-长链酰基氨基酸衍生的酰氯和氨基酸通过肖顿-鲍曼反应等制备;或者通过氨基酸二肽如谷氨酰谷氨酸与酰氯反应。优选采用PCT/CN2022/107270公开的相关制备方法获得,在此,将相关内容一并引入。N-long-chain acyl amino acid dipeptide can be prepared from acyl chloride derived from N-long-chain acyl amino acid and amino acid by Schotten-Bowman reaction, etc.; or by reacting amino acid dipeptide such as glutamylglutamic acid with acyl chloride. Preferably, it is obtained by the relevant preparation method disclosed in PCT/CN2022/107270, and the relevant content is introduced here.
N-长链酰基氨基酸二肽中的N-长链酰基选自辛酰基、癸酰基、十一烷酰基、月桂酰基、肉豆蔻酰基、十五烷酰基、棕榈酰基、硬脂酰基、油酰基、亚油酰基、异硬脂酰基、椰子油脂肪酰基、棕榈油脂肪酰基中的一种或多种,优选椰子油脂肪酰基或月桂酰基,最优选月桂酰基;The N-long-chain acyl group in the N-long-chain acyl amino acid dipeptide is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
所述N-长链酰基氨基酸二肽中的氨基酸来源于丙氨酸、甘氨酸、谷氨酸、肌氨酸、精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种,优选L-丙氨酸。本发明优选N-长链酰基-L-丙氨酸二肽,尤其是月桂酰丙氨酰丙氨酸。 The amino acid in the N-long-chain acyl amino acid dipeptide is derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl) taurine, preferably L-alanine. The present invention preferably uses N-long-chain acyl-L-alanine dipeptide, especially lauroyl alanyl alanine.
N-长链酰基氨基酸二肽的引入可以大大降低原料使用量(即,使用更少量的N-长链酰基氨基酸即可形成凝胶),也能够一定程度提升凝胶的耐热性能和耐寒性能,提升凝胶的挤出和截断性能。The introduction of N-long-chain acyl amino acid dipeptide can greatly reduce the amount of raw materials used (i.e., a smaller amount of N-long-chain acyl amino acid can be used to form a gel), and can also improve the heat resistance and cold resistance of the gel to a certain extent, and improve the extrusion and truncation performance of the gel.
优选的,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在20wt%以上,优选21wt%、22wt%、23wt%、24wt%、25wt%、26wt%、27wt%、28wt%以上。如果用量过低,则难以获得凝胶。具体加入量,主要根据N-长链酰基氨基酸二肽含量进行调整,N-长链酰基氨基酸二肽含量越高,则相应N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和越低。Preferably, the total weight percentage of N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide is above 20wt%, preferably above 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%. If the dosage is too low, it is difficult to obtain a gel. The specific amount added is mainly adjusted according to the content of N-long-chain acyl amino acid dipeptide. The higher the content of N-long-chain acyl amino acid dipeptide, the lower the total weight percentage of the corresponding N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide.
N-长链酰基氨基酸二肽重量百分含量在0.5wt%以上,优选在0.75wt%、1wt%、1.5wt%、2wt%以上。The weight percentage of N-long-chain acyl amino acid dipeptide is above 0.5wt%, preferably above 0.75wt%, 1wt%, 1.5wt%, 2wt%.
N-长链酰基氨基酸与N-长链酰基氨基酸二肽重量比为20:1至1.5:1,优选15:1至3:1,更优选10:1至6:1。N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量比值例如为20、19、18、17、16、15、14、13、12、11、10、9、8、7、6、5、4、3。The weight ratio of N-long chain acyl amino acid to N-long chain acyl amino acid dipeptide is 20: 1 to 1.5: 1, preferably 15: 1 to 3: 1, more preferably 10: 1 to 6: 1. The weight ratio of N-long chain acyl amino acid to N-long chain acyl amino acid dipeptide is, for example, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3.
组分(a)N-长链酰基氨基酸重量百分含量在55wt%以下,优选54wt%、53wt%、52wt%、51wt%、50wt%、49wt%、48wt%、47wt%、46wt%、45wt%、44wt%、43wt%、42wt%、41wt%、40wt%以下,如果用量过高,则凝胶偏硬,不利于挤出和截断。The weight percentage of component (a) N-long-chain acylamino acid is below 55wt%, preferably 54wt%, 53wt%, 52wt%, 51wt%, 50wt%, 49wt%, 48wt%, 47wt%, 46wt%, 45wt%, 44wt%, 43wt%, 42wt%, 41wt%, 40wt% or less. If the dosage is too high, the gel will be too hard, which is not conducive to extrusion and cutting.
组分(b)碱性氨基酸重量百分含量在10wt%以上,优选11wt%、12wt%、13wt%、14wt%、15wt%、16wt%、17wt%以上。优选的,碱性氨基酸以足以部分或完全中和N-长链酰基氨基酸和N-长链酰基氨基酸二肽的量存在,例如可以参照前述实施方式中碱性氨基酸的加入量。当中和度小于100%,且组合物含有N-长链酰基氨基酸二肽时,原料使用量(指N-长链酰基氨基酸及二肽)可以降到最低,产品硬度也相对达到最低,方便凝胶更容易、轻松的罐装。The weight percentage of the basic amino acid of component (b) is above 10wt%, preferably above 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%. Preferably, the basic amino acid is present in an amount sufficient to partially or completely neutralize the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide, for example, the amount of basic amino acid added in the aforementioned embodiment can be referred to. When the degree of neutralization is less than 100% and the composition contains the N-long-chain acyl amino acid dipeptide, the amount of raw materials used (referring to the N-long-chain acyl amino acid and dipeptide) can be reduced to a minimum, and the hardness of the product is relatively minimized, which facilitates easier and easier canning of the gel.
在一个实施方式中,提供一种凝胶组合物。该组合物包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水。In one embodiment, a gel composition is provided, which comprises (a) an N-long-chain acylamino acid, (e) an inorganic base, and (c) water.
组分(a)、(c)参见其他实施方式中的相关描述。组分(e)无机碱选自氢氧化钠、氢氧化钾中的一种或多种,优选氢氧化钠。一般而言,采用常规的氢氧化钠即可,并无特殊要求,如果采用氢氧化钠溶液, 则用量指的是氢氧化钠的用量,而非氢氧化钠溶液的用量。Components (a) and (c) refer to the relevant descriptions in other embodiments. Component (e) inorganic base is selected from one or more of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide. Generally speaking, conventional sodium hydroxide can be used without special requirements. If sodium hydroxide solution is used, The dosage refers to the dosage of sodium hydroxide, not the dosage of sodium hydroxide solution.
对于上述组分(a)和(e),也可以直接添加相应N-长链酰基氨基酸的盐,其与分别添加组分(a)和(e)并无本质区别,也涵盖在本发明保护的范围内。For the above components (a) and (e), the corresponding salts of N-long-chain acylamino acids may also be directly added, which is not essentially different from adding components (a) and (e) separately, and is also covered by the scope of protection of the present invention.
组分(a)N-长链酰基氨基酸重量百分含量在40wt%以上,优选43wt%以上,更优选45wt%以上。如果用量过低,则难以获得凝胶。The weight percentage of component (a) N-long chain acylamino acid is above 40 wt%, preferably above 43 wt%, more preferably above 45 wt%. If the amount is too low, it is difficult to obtain a gel.
组分(a)N-长链酰基氨基酸重量百分含量在75wt%以下,优选70wt%、68wt%、65wt%、64wt%、63wt%、62wt%、61wt%、60wt%、59wt%、58wt%、57wt%、56wt%、55wt%以下,如果用量过高,则凝胶偏硬,不利于挤出和截断。The weight percentage of component (a) N-long-chain acylamino acid is below 75wt%, preferably below 70wt%, 68wt%, 65wt%, 64wt%, 63wt%, 62wt%, 61wt%, 60wt%, 59wt%, 58wt%, 57wt%, 56wt%, 55wt%. If the dosage is too high, the gel will be too hard, which is not conducive to extrusion and cutting.
组分(e)无机碱重量百分含量在5.5wt%以上,优选6wt%以上,更优选6.5wt%以上。优选的,无机碱以足以部分或完全中和N-长链酰基氨基酸的量存在。The weight percentage of the inorganic base of component (e) is above 5.5 wt%, preferably above 6 wt%, more preferably above 6.5 wt%. Preferably, the inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acylamino acid.
在一个实施方式中,提供一种凝胶组合物。该组合物包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,其中,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上。In one embodiment, a gel composition is provided, which comprises (a) N-long-chain acylamino acid, (e) inorganic base, and (c) water, wherein the weight percentage of the N-long-chain acylamino acid is greater than 30 wt%, preferably greater than 33 wt%, and more preferably greater than 35 wt%.
优选的,无机碱以足以部分或完全中和N-长链酰基氨基酸的量存在。在一优选方案中,中和度在85%以上,更优选中和度在88%以上。例如中和度为86%、87%、88%、89%、90%、91%、92%、93%、94%、95%、96%、97%、98%。Preferably, the inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acylamino acid. In a preferred embodiment, the degree of neutralization is above 85%, more preferably above 88%. For example, the degree of neutralization is 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%.
进一步的,从摩尔比的角度,N-长链酰基氨基酸与无机碱的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。示例性的,当N-长链酰基氨基酸为1mol时,无机碱为0.98、0.97、0.96、0.95、0.94、0.93、0.92、0.91、0.90、0.89、0.88、0.87、0.86或0.85mol。Further, from the perspective of molar ratio, the molar ratio of N-long chain acyl amino acid to inorganic base is 1: 0.98 to 1: 0.85, preferably 1: 0.96 to 1: 0.88, more preferably 1: 0.95 to 1: 0.90. Exemplarily, when the N-long chain acyl amino acid is 1 mol, the inorganic base is 0.98, 0.97, 0.96, 0.95, 0.94, 0.93, 0.92, 0.91, 0.90, 0.89, 0.88, 0.87, 0.86 or 0.85 mol.
本发明出人意料的发现,中和度在85%以上且小于100%时,组合物体系内含有少量N-长链酰基氨基酸和/或N-长链酰基氨基酸二肽,能够大大降低原料使用量,使得凝胶更软,提升凝胶的挤出和截断性能。The present invention unexpectedly discovered that when the degree of neutralization is above 85% and less than 100%, a small amount of N-long-chain acyl amino acid and/or N-long-chain acyl amino acid dipeptide is contained in the composition system, which can greatly reduce the amount of raw materials used, make the gel softer, and improve the extrusion and cutting performance of the gel.
在一个实施方式中,提供一种凝胶组合物。该组合物包含(a)N- 长链酰基氨基酸,(e)无机碱,(c)水,(d)N-长链酰基氨基酸二肽。组分(a)、(e)、(c)、(d)参见其他实施方式中的相关描述。In one embodiment, a gel composition is provided. The composition comprises (a) N- Long-chain acyl amino acid, (e) inorganic base, (c) water, (d) N-long-chain acyl amino acid dipeptide. Components (a), (e), (c), (d) refer to the relevant descriptions in other embodiments.
N-长链酰基氨基酸二肽的引入可以大大降低原料使用量(即,使用更少量的N-长链酰基氨基酸即可形成凝胶),也能够一定程度提升凝胶的耐热和耐寒性能,提升凝胶的挤出和截断性能。The introduction of N-long-chain acyl amino acid dipeptide can greatly reduce the amount of raw materials used (i.e., a smaller amount of N-long-chain acyl amino acid can be used to form a gel), and can also improve the heat and cold resistance of the gel to a certain extent, and improve the extrusion and truncation performance of the gel.
优选的,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在30wt%以上,优选31wt%、32wt%、33wt%、34wt%、35wt%、36wt%、37wt%、38wt%、39wt%以上。如果用量过低,则难以获得凝胶。具体加入量,主要根据N-长链酰基氨基酸二肽含量进行调整,N-长链酰基氨基酸二肽含量越高,则相应N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和越低。Preferably, the total weight percentage of N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide is above 30wt%, preferably above 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%. If the dosage is too low, it is difficult to obtain a gel. The specific amount added is mainly adjusted according to the content of N-long-chain acyl amino acid dipeptide. The higher the content of N-long-chain acyl amino acid dipeptide, the lower the total weight percentage of the corresponding N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide.
N-长链酰基氨基酸二肽重量百分含量在0.5wt%以上,优选在0.75wt%、1wt%、1.5wt%、2wt%以上。The weight percentage of N-long-chain acyl amino acid dipeptide is above 0.5wt%, preferably above 0.75wt%, 1wt%, 1.5wt%, 2wt%.
N-长链酰基氨基酸与N-长链酰基氨基酸二肽重量比为20:1至1.5:1,优选15:1至3:1,更优选10:1至6:1。N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量比值例如为20、19、18、17、16、15、14、13、12、11、10、9、8、7、6、5、4、3。The weight ratio of N-long chain acyl amino acid to N-long chain acyl amino acid dipeptide is 20: 1 to 1.5: 1, preferably 15: 1 to 3: 1, more preferably 10: 1 to 6: 1. The weight ratio of N-long chain acyl amino acid to N-long chain acyl amino acid dipeptide is, for example, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3.
组分(a)N-长链酰基氨基酸重量百分含量在75wt%以下,优选70wt%、68wt%、65wt%、64wt%、63wt%、62wt%、61wt%、60wt%、59wt%、58wt%、57wt%、56wt%、55wt%以下,如果用量过高,则凝胶偏硬,不利于挤出和截断。The weight percentage of component (a) N-long-chain acylamino acid is below 75wt%, preferably below 70wt%, 68wt%, 65wt%, 64wt%, 63wt%, 62wt%, 61wt%, 60wt%, 59wt%, 58wt%, 57wt%, 56wt%, 55wt%. If the dosage is too high, the gel will be too hard, which is not conducive to extrusion and cutting.
组分(e)无机碱重量百分含量在4wt%以上,优选4.5wt%以上,更优选5wt%以上。优选的,无机碱以足以部分或完全中和N-长链酰基氨基酸和N-长链酰基氨基酸二肽的量存在。The weight percentage of component (e) inorganic base is above 4wt%, preferably above 4.5wt%, more preferably above 5wt%. Preferably, the inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acylamino acid and the N-long-chain acylamino acid dipeptide.
在各实施方式中,未论述的详情在内容不冲突的情况下,可以参照其他实施方式的相关指导。In each implementation manner, if the details not discussed do not conflict with the content, reference can be made to the relevant instructions of other implementation manners.
在各实施方式中,本发明的组合物不含或基本不含增稠剂。所谓“基本不含”,是指组合物中增稠剂的量不会显著影响产品的性能,增稠剂的量不足以形成凝胶,即本发明的凝胶形成并非源于增稠剂的作用。优选的,本发明的组合物完全不含有传统的增稠剂。如背 景技术中所述,传统增稠剂/凝胶化剂对产品性能(颜色、泡沫、功效、使用感受等)有不利影响。In various embodiments, the composition of the present invention contains no or substantially no thickener. By “substantially no”, it is meant that the amount of thickener in the composition does not significantly affect the performance of the product, and the amount of thickener is insufficient to form a gel, i.e., the gel formation of the present invention is not due to the action of the thickener. Preferably, the composition of the present invention does not contain any traditional thickener at all. As described in the technical specification, traditional thickeners/gelling agents have adverse effects on product performance (color, foam, efficacy, user experience, etc.).
进一步的,本发明组合物不含有纤维素类、粘多糖类、聚乙烯醇类、胶质类、聚丙烯酸钠类、聚乙烯基吡咯烷酮类、乙烯基聚合物类等增稠剂。例如本发明组合物不含有淀粉、明胶、海藻酸钠、瓜尔胶、甲壳胶、阿拉伯树胶、黄原胶、大豆蛋白胶、聚丙烯酰胺、聚乙烯醇、聚乙烯吡咯烷酮、改性石蜡树脂、卡波树脂、丁苯橡胶等。Furthermore, the composition of the present invention does not contain thickeners such as cellulose, mucopolysaccharides, polyvinyl alcohols, colloids, sodium polyacrylates, polyvinyl pyrrolidones, vinyl polymers, etc. For example, the composition of the present invention does not contain starch, gelatin, sodium alginate, guar gum, chitosan, gum arabic, xanthan gum, soy protein gum, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, modified paraffin resin, carbomer resin, styrene-butadiene rubber, etc.
进一步的,本发明组合物不涉及AES体系,不需要氯化钠增稠,所以组合物中不含或基本不含氯化钠,所谓“基本不含”,是指组合物中氯化钠的量不会显著影响产品的性能,氯化钠的量不足以形成凝胶。Furthermore, the composition of the present invention does not involve an AES system and does not require sodium chloride thickening, so the composition does not contain or substantially contains no sodium chloride. The so-called "substantially contains no" means that the amount of sodium chloride in the composition will not significantly affect the performance of the product, and the amount of sodium chloride is insufficient to form a gel.
在各实施方式中,本发明的凝胶组合物pH值落在弱酸性至弱碱性对应用有利。具体而言,按GB/T 13531.1中规定的稀释法,测凝胶组合物的pH值,pH值在4.5以上,优选5以上,更优选5.5以上;且pH值在12以下,优选11以下,更优选10以下。In various embodiments, the pH value of the gel composition of the present invention falls within the range of weak acidity to weak alkalinity, which is advantageous for application. Specifically, the pH value of the gel composition is measured by the dilution method specified in GB/T 13531.1, and the pH value is above 4.5, preferably above 5, and more preferably above 5.5; and the pH value is below 12, preferably below 11, and more preferably below 10.
在各实施方式中,本发明的凝胶组合物形成凝胶后,利用日本RHEOTECH硬度计检测,在荷重2kg、适配器20mmφ、针入速度6cm/min、针入距离10mm的检测条件下,硬度在1.80以下,优选在1.70、1.60、1.50、1.40、1.30、1.20、1.10或1.00以下,更优选在0.90、0.80、0.70、0.50、0.40、0.30或0.20以下,凝胶硬度越低,越有利于管状产品的充填。In each embodiment, after the gel composition of the present invention forms a gel, the hardness is tested by a Japanese RHEOTECH hardness tester under the test conditions of a load of 2 kg, an adapter of 20 mmφ, a needle penetration speed of 6 cm/min, and a needle penetration distance of 10 mm. The hardness is below 1.80, preferably below 1.70, 1.60, 1.50, 1.40, 1.30, 1.20, 1.10 or 1.00, and more preferably below 0.90, 0.80, 0.70, 0.50, 0.40, 0.30 or 0.20. The lower the gel hardness, the more conducive it is to filling of tubular products.
本发明还提供一种凝胶,其由前述凝胶组合物制备得到。优选的,本发明的凝胶具有良好的耐热性能和耐寒性能,具体而言,凝胶在40±1℃保持24h,恢复室温后可正常使用;凝胶在-8±2℃保持24h,恢复室温后可正常使用。所述“可正常使用”,是指凝胶外观及性能无明显变化,不影响使用。The present invention also provides a gel, which is prepared from the above-mentioned gel composition. Preferably, the gel of the present invention has good heat resistance and cold resistance. Specifically, the gel is kept at 40±1°C for 24 hours and can be used normally after returning to room temperature; the gel is kept at -8±2°C for 24 hours and can be used normally after returning to room temperature. The "can be used normally" means that the appearance and performance of the gel have no obvious changes and do not affect the use.
本发明的凝胶可以作为清洁凝胶、护肤凝胶、洗发凝胶、剃须凝胶、卸妆凝胶、按摩凝胶、化妆用凝胶、口腔用凝胶或多功能凝胶。所述多功能性,是指可以用于多种场景、具有多种用途。例如可以作为洗手产品、沐浴产品、洗发产品、卸妆产品使用,也可以 作为牙膏使用;在户外,可以作为各类器具如野外餐具的清洁剂使用。The gel of the present invention can be used as a cleansing gel, a skin care gel, a shampoo gel, a shaving gel, a makeup removal gel, a massage gel, a cosmetic gel, an oral gel or a multifunctional gel. The multifunctionality means that it can be used in a variety of scenarios and has a variety of uses. For example, it can be used as a hand washing product, a bath product, a shampoo product, a makeup removal product, or a multifunctional gel. It can be used as toothpaste; outdoors, it can be used as a cleaner for various utensils such as outdoor tableware.
本发明还提供一种牙膏,其含有前述的凝胶组合物。作为牙膏产品,根据产品性能的需要,还可以加入摩擦剂、保湿剂、甜味剂、香精、防腐剂、着色剂等。The present invention also provides a toothpaste containing the aforementioned gel composition. As a toothpaste product, abrasives, moisturizers, sweeteners, flavors, preservatives, colorants, etc. may also be added according to the requirements of product performance.
本发明还提供一种化妆品,其含有前述的凝胶组合物。作为化妆品产品,根据产品性能的需要,还可以加入保湿剂、香精、防腐剂、着色剂、油类、悬浮颗粒等。所述悬浮颗粒选自油不溶性的固体颗粒或油不混溶液体。其中所述油不溶性的固体颗粒包括云母、淀粉、氧化锌、二氧化钛、滑石粉和有机硅弹性体。所述油不混溶液体包括甘油、水和多元醇。The present invention also provides a cosmetic comprising the aforementioned gel composition. As a cosmetic product, moisturizers, flavors, preservatives, colorants, oils, suspended particles, etc. may also be added according to the requirements of product performance. The suspended particles are selected from oil-insoluble solid particles or oil-immiscible liquids. The oil-insoluble solid particles include mica, starch, zinc oxide, titanium dioxide, talc and silicone elastomer. The oil-immiscible liquid includes glycerin, water and polyols.
本发明还提供一种清洁产品,其含有前述的凝胶组合物。作为清洁产品,根据产品性能的需要,还可以加入柔软剂、螯合剂、防腐剂、甘油和香精等。The present invention also provides a cleaning product, which contains the aforementioned gel composition. As the cleaning product, softeners, chelating agents, preservatives, glycerin and essences can also be added according to the requirements of product performance.
本发明还提供一种极简配方的清洁产品,其仅含有前述(a)N-长链酰基氨基酸,(b)碱性氨基酸/(e)无机碱,(c)水。或者,仅含有前述(a)N-长链酰基氨基酸,(b)碱性氨基酸/(e)无机碱,(c)水及必要的防腐剂和/或甜味剂。The present invention also provides a cleaning product with a minimal formula, which contains only the aforementioned (a) N-long-chain acyl amino acid, (b) basic amino acid/(e) inorganic base, and (c) water. Alternatively, it contains only the aforementioned (a) N-long-chain acyl amino acid, (b) basic amino acid/(e) inorganic base, (c) water and necessary preservatives and/or sweeteners.
本发明提供一种凝胶组合物的制备方法,其包含如下步骤:在75-90℃,优选80-85℃条件下,混合(a)、(b)或(e)、(c)和任选的(d)。The present invention provides a method for preparing a gel composition, comprising the following steps: mixing (a), (b) or (e), (c) and optionally (d) at 75-90°C, preferably 80-85°C.
优选的,先将(b)或(e)与(c)混合得到溶液I,之后在75-90℃、优选80-85℃条件下使得(a)和任选的(d)熔融得到溶液II,最后,在75-90℃、优选80-85℃条件下,将溶液I与溶液II混合。Preferably, (b) or (e) is first mixed with (c) to obtain solution I, then (a) and optional (d) are melted at 75-90°C, preferably 80-85°C to obtain solution II, and finally, solution I is mixed with solution II at 75-90°C, preferably 80-85°C.
本发明还提供一种赋予清洁组合物凝胶特性的方法,清洁组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上,碱性氨基酸重量百分含量在15wt%以上,优选17wt%以上,更优选20wt%以上;The present invention also provides a method for imparting gel properties to a cleaning composition, the cleaning composition comprising (a) an N-long-chain acyl amino acid, and (b) a basic amino acid, wherein the weight percentage of the N-long-chain acyl amino acid is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the basic amino acid is greater than 15 wt %, preferably greater than 17 wt %, more preferably greater than 20 wt %;
或者,包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽 的重量百分含量总和在20wt%以上,优选23wt%以上,更优选25wt%以上,碱性氨基酸重量百分含量在10wt%以上,优选12wt%以上,更优选14wt%以上;Alternatively, the invention comprises (a) an N-long chain acyl amino acid, (b) a basic amino acid, and (d) an N-long chain acyl amino acid dipeptide, wherein the N-long chain acyl amino acid and the N-long chain acyl amino acid dipeptide The total weight percentage of is more than 20wt%, preferably more than 23wt%, more preferably more than 25wt%, the weight percentage of basic amino acids is more than 10wt%, preferably more than 12wt%, more preferably more than 14wt%;
或者,清洁组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,其中,N-长链酰基氨基酸重量百分含量在20wt%以上,优选23wt%以上,更优选25wt%以上,N-长链酰基氨基酸与碱性氨基酸的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid and (b) a basic amino acid, wherein the weight percentage of the N-long-chain acyl amino acid is above 20 wt %, preferably above 23 wt %, more preferably above 25 wt %, and the molar ratio of the N-long-chain acyl amino acid to the basic amino acid is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
组分(a)、(b)、(d)及其用量参见其他实施方式中的相关描述。当采用上述组分时,可以赋予清洁组合物凝胶特性。Components (a), (b), (d) and their amounts are as described in other embodiments. When the above components are used, gel properties can be imparted to the cleaning composition.
本发明还提供另一种赋予清洁组合物凝胶特性的方法,清洁组合物包含(a)N-长链酰基氨基酸,(e)无机碱,其中,N-长链酰基氨基酸重量百分含量在40wt%以上,优选43wt%以上,更优选45wt%以上,无机碱重量百分含量在5.5wt%以上,优选6wt%以上,更优选6.5wt%以上;The present invention also provides another method for imparting gel properties to a cleaning composition, the cleaning composition comprising (a) an N-long-chain acylamino acid, and (e) an inorganic base, wherein the weight percentage of the N-long-chain acylamino acid is greater than 40 wt %, preferably greater than 43 wt %, more preferably greater than 45 wt %, and the weight percentage of the inorganic base is greater than 5.5 wt %, preferably greater than 6 wt %, more preferably greater than 6.5 wt %;
或者,包含(a)N-长链酰基氨基酸,(e)无机碱,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在30wt%以上,优选33wt%以上,更优选35wt%以上,无机碱重量百分含量在4wt%以上,优选4.5wt%以上,更优选5wt%以上;Alternatively, it comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the inorganic base is greater than 4 wt %, preferably greater than 4.5 wt %, more preferably greater than 5 wt %;
或者,清洁组合物包含(a)N-长链酰基氨基酸,(e)无机碱,其中,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上,N-长链酰基氨基酸与无机碱的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid and (e) an inorganic base, wherein the weight percentage of the N-long-chain acyl amino acid is above 30 wt %, preferably above 33 wt %, more preferably above 35 wt %, and the molar ratio of the N-long-chain acyl amino acid to the inorganic base is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
组分(a)、(e)、(d)及其用量参见其他实施方式中的相关描述。当采用上述组分时,可以赋予清洁组合物凝胶特性。Components (a), (e), (d) and their usage amounts refer to the related descriptions in other embodiments. When the above components are used, gel properties can be imparted to the cleaning composition.
下面结合附图和实施例对本发明作进一步的阐述,应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后本领域技术人员可以对本发明做各种改动或修改,这些等价同样落于本申请所附权利要求书所限 定的范围。The present invention is further described below in conjunction with the accompanying drawings and embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. In addition, it should be understood that after reading the contents of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalents also fall within the scope of the claims attached to this application. A certain range.
下面将结合具体实施例进一步描述本发明。The present invention will be further described below with reference to specific embodiments.
实施例Example
将碱性氨基酸或氢氧化钠与水混合得到溶液I;在85℃条件下使得N-长链酰基氨基酸(N-长链酰基氨基酸二肽)熔融得到溶液II;最后,在85℃条件下,边搅拌边将溶液I逐渐加入溶液II,最终形成凝胶(部分实施例为溶液),详细记录于表1。实施例1-7的凝胶外观见图1;实施例8-10的凝胶外观见图2;实施例11-12的凝胶外观见图3;实施例13-15的凝胶外观见图4;实施例16的凝胶外观见图5。Mix basic amino acid or sodium hydroxide with water to obtain solution I; melt N-long chain acyl amino acid (N-long chain acyl amino acid dipeptide) at 85°C to obtain solution II; finally, gradually add solution I to solution II at 85°C while stirring to finally form a gel (some embodiments are solutions), which is recorded in detail in Table 1. The appearance of the gels of Examples 1-7 is shown in Figure 1; the appearance of the gels of Examples 8-10 is shown in Figure 2; the appearance of the gels of Examples 11-12 is shown in Figure 3; the appearance of the gels of Examples 13-15 is shown in Figure 4; the appearance of the gel of Example 16 is shown in Figure 5.
如图1所示,N-月桂酰-L-丙氨酸重量百分含量达到30wt%时,已经开始出现凝胶,随着N-月桂酰-L-丙氨酸含量的增加,凝胶逐渐增多,当达到33wt%时,所有溶液全部成为凝胶。As shown in FIG1 , when the weight percentage of N-lauroyl-L-alanine reaches 30wt%, gel begins to appear. As the content of N-lauroyl-L-alanine increases, the amount of gel gradually increases. When the content reaches 33wt%, all the solutions become gel.
如图2所示,如果将精氨酸替换为氢氧化钠,N-月桂酰-L-丙氨酸重量百分含量35wt%时,产品仍然是溶液;当N-月桂酰-L-丙氨酸重量百分含量40wt%时,大部分形成凝胶,仅有少量溶液;进一步增加N-月桂酰-L-丙氨酸含量,则全部形成凝胶。As shown in Figure 2, if arginine is replaced with sodium hydroxide, when the weight percentage of N-lauroyl-L-alanine is 35wt%, the product is still a solution; when the weight percentage of N-lauroyl-L-alanine is 40wt%, most of it forms a gel, with only a small amount of solution; further increasing the content of N-lauroyl-L-alanine, all of it forms a gel.
如图3所示,如果将N-月桂酰-L-丙氨酸替换为月桂酰肌氨酸,则月桂酰肌氨酸重量百分含量33wt%时,开始出现凝胶,增加含量至35%时,完全形成凝胶。As shown in FIG3 , if N-lauroyl-L-alanine is replaced by lauroyl sarcosine, gel begins to appear when the weight percentage of lauroyl sarcosine is 33 wt %, and gel is completely formed when the content is increased to 35%.
如图4所示,如果将精氨酸替换为赖氨酸,同样可以形成凝胶。As shown in FIG4 , if arginine is replaced by lysine, a gel can also be formed.
如图5所示,如果进一步引入月桂酰丙氨酰丙氨酸(月桂酰丙氨酸二肽),则N-月桂酰-L-丙氨酸与二肽总含量25wt%时,已经可以形成凝胶。As shown in FIG5 , if lauroyl alanyl alanine (lauroyl alanine dipeptide) is further introduced, a gel can be formed when the total content of N-lauroyl-L-alanine and dipeptide is 25 wt %.
进一步研究发现,当中和度在85%以上且小于100%时,同样能够大大降低长链酰基氨基酸使用量,且凝胶更软(参见实施例17-23)。当添加少量二肽且不完全中和(实施例20)时,能够进一步降低长链酰基氨基酸的添加量。Further research found that when the degree of neutralization is above 85% and less than 100%, the amount of long-chain acyl amino acids used can also be greatly reduced, and the gel is softer (see Examples 17-23). When a small amount of dipeptide is added and incompletely neutralized (Example 20), the amount of long-chain acyl amino acids added can be further reduced.
表1.



*1.通过月桂酰肌氨酸钠水溶液与盐酸反应制备获得。
*2.由赖氨酸盐酸盐水溶液与氢氧化钠反应制备得到。
*3.二肽指月桂酰丙氨酰丙氨酸,“N-月桂酰-L-丙氨酸+二肽”参照
PCT/CN2022/107270实施例503#、实施例6的方法制备得到。
*4.实施例(VI)中除N-月桂酰-L-丙氨酸和精氨酸外,余量为水,摩尔比是指N-
月桂酰-L-丙氨酸:精氨酸。
*5.实施例20中长链酰基氨基酸的组成为:95%N-月桂酰-L-丙氨酸+5%月桂酰
丙氨酸二肽。
Table 1.



*1. Prepared by reacting sodium lauroyl sarcosinate aqueous solution with hydrochloric acid.
*2. Prepared by reacting lysine hydrochloride aqueous solution with sodium hydroxide.
*3.Dipeptide refers to lauroyl alanine, "N-lauroyl-L-alanine + dipeptide" refers to
Prepared by the method of Example 503# and Example 6 of PCT/CN2022/107270.
*4. In Example (VI), except for N-lauroyl-L-alanine and arginine, the balance is water, and the molar ratio refers to N-
Lauroyl-L-Alanine:Arginine.
*5. The composition of the long-chain acyl amino acid in Example 20 is: 95% N-lauroyl-L-alanine + 5% lauroyl alanine dipeptide.
性能评价Performance Evaluation
触感:3名专业评测人员分别评测,综合判断得出。Touch: 3 professional reviewers evaluated separately and made comprehensive judgment.
硬度:测试仪器:日本RHEOTECH硬度计/流变仪,测试条件:荷重2kg(选择2K/20N),适配器20mmφ,针入速度6cm/min,针入距离10mm。Hardness: Test instrument: Japan RHEOTECH hardness tester/rheometer, test conditions: load 2kg (select 2K/20N), adapter 20mmφ, needle penetration speed 6cm/min, needle penetration distance 10mm.
pH:按GB/T 13531.1中规定的稀释法,测所获得溶液的pH值。pH: Measure the pH value of the solution obtained by the dilution method specified in GB/T 13531.1.
耐热性测试:40℃保持24h,60℃、70℃、80℃各保持1h,之后恢复室温,观察凝胶在高温条件下的稳定性以及恢复室温后能否正常使用。Heat resistance test: maintain at 40℃ for 24h, 60℃, 70℃, 80℃ for 1h respectively, then return to room temperature to observe the stability of the gel under high temperature conditions and whether it can be used normally after returning to room temperature.
耐寒性测试:-6℃保持24h,-18℃保持12h,之后恢复室温,观察凝胶在低温条件下的稳定性以及恢复室温后能否正常使用。Cold resistance test: keep at -6℃ for 24h, keep at -18℃ for 12h, then return to room temperature to observe the stability of the gel under low temperature conditions and whether it can be used normally after returning to room temperature.
稳定性测试:-6℃、50℃、Cycle试验、耐光试验各做一个月后停止观察。其中,Cycle试验:0℃×2日→25℃×2日→40℃×2日循环;耐光试验:荧光灯照射条件:约23000Lux/day、25℃。Stability test: -6℃, 50℃, cycle test, light resistance test were performed for one month and then stopped for observation. Cycle test: 0℃×2 days→25℃×2 days→40℃×2 days cycle; light resistance test: fluorescent light irradiation conditions: about 23000Lux/day, 25℃.
40℃观察3个月,5℃观察3个月,常温观察3个月。Observe for 3 months at 40℃, 3 months at 5℃, and 3 months at room temperature.
测试结果记录于表2。The test results are recorded in Table 2.
表2.



-:未测试
◎:凝胶非常稳定,恢复室温可正常使用,恢复速度快
○:凝胶稳定,恢复室温可正常使用,恢复速度较快
△:凝胶不太稳定,恢复室温后形貌发生变化,性能有差异
×:凝胶不稳定,恢复室温后不能正常使用
Table 2.



-: Not tested ◎: The gel is very stable and can be used normally after returning to room temperature. The recovery speed is fast ○: The gel is stable and can be used normally after returning to room temperature. The recovery speed is fast △: The gel is not very stable. The morphology changes after returning to room temperature, and the performance is different ×: The gel is unstable and cannot be used normally after returning to room temperature
从实验的综合结果来看,N-长链酰基氨基酸与精氨酸的组合稳定性非常好,其中,N-月桂酰-L-丙氨酸与精氨酸的组合在耐热、耐寒、稳定性方面表现良好,且清洁力优异;月桂酰肌氨酸与精氨酸的组合在耐热、耐寒、稳定性方面表现优异,但清洁力有所欠缺。Judging from the comprehensive results of the experiment, the combination of N-long-chain acyl amino acids and arginine has very good stability. Among them, the combination of N-lauroyl-L-alanine and arginine performs well in heat resistance, cold resistance, stability, and excellent cleaning power; the combination of lauroyl sarcosine and arginine performs well in heat resistance, cold resistance, and stability, but lacks cleaning power.
N-月桂酰-L-丙氨酸与赖氨酸的组合,稳定性较差(尤其是低温稳定性);N-月桂酰-L-丙氨酸与氢氧化钠的组合稳定性中等。The combination of N-lauroyl-L-alanine and lysine has poor stability (especially low temperature stability); the combination of N-lauroyl-L-alanine and sodium hydroxide has moderate stability.
N-月桂酰-L-丙氨酸、月桂酰丙氨酰丙氨酸(二肽)与精氨酸的组合,性能最佳。一方面,产品在耐热、耐寒、稳定性方面表现优秀;另一方面,其清洁力高,有利于各场景的使用。The combination of N-lauroyl-L-alanine, lauroyl alanyl alanine (dipeptide) and arginine has the best performance. On the one hand, the product has excellent performance in heat resistance, cold resistance and stability; on the other hand, its high cleaning power is conducive to use in various scenarios.
进一步研究发现,当中和度在85%以上且小于100%时,形成的凝胶非常软,更加适合管状产品的充填。当中和度较低时(如85%以下),发现耐热、耐寒循环试验中,有时会出现泛白现象(可能是过量未中和的月桂酰丙氨酸会逐渐析出)。当添加少量二肽且不完全中和(实施例20)时,使用25%左右的长链酰基氨基酸即可形成稳定的软凝胶。Further research found that when the degree of neutralization is above 85% and less than 100%, the gel formed is very soft and more suitable for filling tubular products. When the degree of neutralization is low (such as below 85%), it is found that whitening sometimes occurs in the heat and cold cycle test (it may be that the excessive unneutralized lauroyl alanine will gradually precipitate). When a small amount of dipeptide is added and not completely neutralized (Example 20), a stable soft gel can be formed using about 25% of long-chain acyl amino acids.
此外,本领域的技术人员能够理解,尽管在此所述的一些实施例包括其它实施例中所包括的某些特征而不是其它特征,但是不同实施例的特征的组合意味着处于本发明的范围之内并且形成不同的实施例。例如,在下面的权利要求书中,所要求保护的实施例的任意之一都可以以任意的组合方式来使用。 In addition, those skilled in the art will appreciate that, although some embodiments described herein include certain features included in other embodiments but not other features, the combination of features of different embodiments is meant to be within the scope of the present invention and form different embodiments. For example, in the following claims, any one of the claimed embodiments may be used in any combination.

Claims (29)

  1. 一种凝胶组合物,其特征在于,包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,通过N-长链酰基氨基酸、碱性氨基酸的自增稠形成凝胶;A gel composition, characterized in that it comprises (a) an N-long chain acyl amino acid, (b) a basic amino acid, and (c) water, and forms a gel through self-thickening of the N-long chain acyl amino acid and the basic amino acid;
    或者,包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,(d)N-长链酰基氨基酸二肽,通过N-长链酰基氨基酸、碱性氨基酸、N-长链酰基氨基酸二肽的自增稠形成凝胶;Alternatively, it comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, (c) water, and (d) N-long-chain acyl amino acid dipeptide, and forms a gel through self-thickening of the N-long-chain acyl amino acid, the basic amino acid, and the N-long-chain acyl amino acid dipeptide;
    或者,包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,通过N-长链酰基氨基酸、无机碱的自增稠形成凝胶;Alternatively, the method comprises (a) an N-long-chain acylamino acid, (e) an inorganic base, and (c) water, wherein the gel is formed by self-thickening of the N-long-chain acylamino acid and the inorganic base;
    或者,包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,(d)N-长链酰基氨基酸二肽,通过N-长链酰基氨基酸、无机碱、N-长链酰基氨基酸二肽的自增稠形成凝胶。Alternatively, it comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, (c) water, and (d) an N-long-chain acyl amino acid dipeptide, and forms a gel through self-thickening of the N-long-chain acyl amino acid, the inorganic base, and the N-long-chain acyl amino acid dipeptide.
  2. 一种凝胶组合物,其特征在于,包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,其中,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上,碱性氨基酸重量百分含量在15wt%以上,优选17wt%以上,更优选20wt%以上;A gel composition, characterized in that it comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, and (c) water, wherein the weight percentage of N-long-chain acyl amino acid is greater than 30 wt%, preferably greater than 33 wt%, more preferably greater than 35 wt%, and the weight percentage of basic amino acid is greater than 15 wt%, preferably greater than 17 wt%, more preferably greater than 20 wt%;
    或者,包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在20wt%以上,优选23wt%以上,更优选25wt%以上,碱性氨基酸重量百分含量在10wt%以上,优选12wt%以上,更优选14wt%以上;Alternatively, it comprises (a) an N-long-chain acyl amino acid, (b) a basic amino acid, (c) water, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 20 wt%, preferably greater than 23 wt%, more preferably greater than 25 wt%, and the weight percentage of the basic amino acid is greater than 10 wt%, preferably greater than 12 wt%, more preferably greater than 14 wt%;
    或者,包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(c)水,其中,N-长链酰基氨基酸重量百分含量在20wt%以上,优选23wt%以上,更优选25wt%以上,N-长链酰基氨基酸与碱性氨基酸的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。Alternatively, it comprises (a) N-long-chain acyl amino acid, (b) basic amino acid, and (c) water, wherein the weight percentage of N-long-chain acyl amino acid is above 20wt%, preferably above 23wt%, more preferably above 25wt%, and the molar ratio of N-long-chain acyl amino acid to basic amino acid is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
  3. 一种凝胶组合物,其特征在于,包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,其中,N-长链酰基氨基酸重量百分含量在40wt%以上,优选43wt%以上,更优选45wt%以上,无机碱重量百分含量在 5.5wt%以上,优选6wt%以上,更优选6.5wt%以上;A gel composition, characterized in that it comprises (a) N-long-chain acylamino acid, (e) inorganic base, and (c) water, wherein the weight percentage of the N-long-chain acylamino acid is above 40wt%, preferably above 43wt%, more preferably above 45wt%, and the weight percentage of the inorganic base is above 5.5wt% or more, preferably 6wt% or more, more preferably 6.5wt% or more;
    或者,包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在30wt%以上,优选33wt%以上,更优选35wt%以上,无机碱重量百分含量在4wt%以上,优选4.5wt%以上,更优选5wt%以上;Alternatively, it comprises (a) N-long-chain acyl amino acid, (e) inorganic base, (c) water, and (d) N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of N-long-chain acyl amino acid and N-long-chain acyl amino acid dipeptide is greater than 30wt%, preferably greater than 33wt%, more preferably greater than 35wt%, and the weight percentage of inorganic base is greater than 4wt%, preferably greater than 4.5wt%, more preferably greater than 5wt%;
    或者,包含(a)N-长链酰基氨基酸,(e)无机碱,(c)水,其中,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上,N-长链酰基氨基酸与无机碱的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。Alternatively, it comprises (a) N-long-chain acyl amino acid, (e) inorganic base, and (c) water, wherein the weight percentage of N-long-chain acyl amino acid is above 30wt%, preferably above 33wt%, more preferably above 35wt%, and the molar ratio of N-long-chain acyl amino acid to inorganic base is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
  4. 根据权利要求1-3任一项所述的凝胶组合物,其特征在于,所述N-长链酰基氨基酸中的N-长链酰基来源于碳原子数8~22的饱和或不饱和直链或支链的脂肪酸;The gel composition according to any one of claims 1 to 3, characterized in that the N-long-chain acyl group in the N-long-chain acyl amino acid is derived from a saturated or unsaturated straight-chain or branched fatty acid having 8 to 22 carbon atoms;
    和/或,所述N-长链酰基氨基酸中的氨基酸来源于甘氨酸、丙氨酸、谷氨酸、肌氨酸、天冬氨酸、亮氨酸、异亮氨酸、缬氨酸、苏氨酸、脯氨酸、苯丙氨酸、精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种。And/or, the amino acids in the N-long-chain acyl amino acids are derived from one or more of glycine, alanine, glutamic acid, sarcosine, aspartic acid, leucine, isoleucine, valine, threonine, proline, phenylalanine, arginine, lysine, and (methyl)taurine.
  5. 根据权利要求1-4任一项所述的凝胶组合物,其特征在于,所述N-长链酰基氨基酸中的N-长链酰基选自辛酰基、癸酰基、十一烷酰基、月桂酰基、肉豆蔻酰基、十五烷酰基、棕榈酰基、硬脂酰基、油酰基、亚油酰基、异硬脂酰基、椰子油脂肪酰基、棕榈油脂肪酰基中的一种或多种,优选椰子油脂肪酰基或月桂酰基,最优选月桂酰基;The gel composition according to any one of claims 1 to 4, characterized in that the N-long-chain acyl group in the N-long-chain acyl amino acid is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
    和/或,所述N-长链酰基氨基酸中的氨基酸来源于丙氨酸、甘氨酸、谷氨酸、肌氨酸、精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种,优选丙氨酸,最优选L-丙氨酸。And/or, the amino acid in the N-long-chain acylamino acid is derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
  6. 根据权利要求1-5任一项所述的凝胶组合物,其特征在于,所述碱性氨基酸选自精氨酸、赖氨酸、瓜氨酸、鸟氨酸、肌酸、组氨酸、二氨基丁酸、二氨基丙酸中的一种或多种,优选精氨酸和/或赖氨酸,最优选精氨酸; The gel composition according to any one of claims 1 to 5, characterized in that the basic amino acid is selected from one or more of arginine, lysine, citrulline, ornithine, creatine, histidine, diaminobutyric acid, and diaminopropionic acid, preferably arginine and/or lysine, most preferably arginine;
    和/或,所述无机碱选自氢氧化钠、氢氧化钾中的一种或多种。And/or, the inorganic base is selected from one or more of sodium hydroxide and potassium hydroxide.
  7. 根据权利要求1-6任一项所述的凝胶组合物,其特征在于,所述N-长链酰基氨基酸二肽中的N-长链酰基选自辛酰基、癸酰基、十一烷酰基、月桂酰基、肉豆蔻酰基、十五烷酰基、棕榈酰基、硬脂酰基、油酰基、亚油酰基、异硬脂酰基、椰子油脂肪酰基、棕榈油脂肪酰基中的一种或多种,优选椰子油脂肪酰基或月桂酰基,最优选月桂酰基;The gel composition according to any one of claims 1 to 6, characterized in that the N-long-chain acyl group in the N-long-chain acyl amino acid dipeptide is selected from one or more of octanoyl, decanoyl, undecanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, oleoyl, linoleoyl, isostearoyl, coconut oil fatty acyl, and palm oil fatty acyl, preferably coconut oil fatty acyl or lauroyl, and most preferably lauroyl;
    和/或,所述N-长链酰基氨基酸二肽中的氨基酸来源于丙氨酸、甘氨酸、谷氨酸、肌氨酸、精氨酸、赖氨酸、(甲基)牛磺酸中的一种或多种,优选丙氨酸,最优选L-丙氨酸。And/or, the amino acids in the N-long-chain acyl amino acid dipeptide are derived from one or more of alanine, glycine, glutamic acid, sarcosine, arginine, lysine, (methyl)taurine, preferably alanine, most preferably L-alanine.
  8. 根据权利要求1-7任一项所述的凝胶组合物,其特征在于,所述N-长链酰基氨基酸二肽选自长链酰基甘氨酰甘氨酸、长链酰基谷氨酰谷氨酸、长链酰基丙氨酰丙氨酸、长链酰基肌氨酰肌氨酸中的一种或多种。The gel composition according to any one of claims 1 to 7, characterized in that the N-long-chain acyl amino acid dipeptide is selected from one or more of long-chain acyl glycylglycine, long-chain acyl glutamyl glutamate, long-chain acyl alanyl alanine, and long-chain acyl sarcosyl sarcosine.
  9. 根据权利要求2,4-8任一项所述的凝胶组合物,其特征在于,N-长链酰基氨基酸重量百分含量在55wt%以下,优选在50wt%以下,更优选在45wt%以下。The gel composition according to any one of claims 2, 4-8, characterized in that the weight percentage of N-long-chain acylamino acid is below 55wt%, preferably below 50wt%, and more preferably below 45wt%.
  10. 根据权利要求3-8任一项所述的凝胶组合物,其特征在于,N-长链酰基氨基酸重量百分含量在75wt%以下,优选在65wt%以下,更优选在60wt%以下。The gel composition according to any one of claims 3 to 8, characterized in that the weight percentage of the N-long-chain acylamino acid is below 75 wt%, preferably below 65 wt%, and more preferably below 60 wt%.
  11. 根据权利要求1-10任一项所述的凝胶组合物,其特征在于,组合物中N-长链酰基氨基酸二肽重量百分含量在0.5wt%以上,优选在0.75wt%以上,更优选在1wt%以上;The gel composition according to any one of claims 1 to 10, characterized in that the weight percentage of the N-long-chain acyl amino acid dipeptide in the composition is above 0.5 wt%, preferably above 0.75 wt%, and more preferably above 1 wt%;
    和/或,N-长链酰基氨基酸与N-长链酰基氨基酸二肽重量比为20:1至1.5:1,优选15:1至3:1,更优选10:1至6:1。And/or, the weight ratio of N-long-chain acyl amino acid to N-long-chain acyl amino acid dipeptide is 20:1 to 1.5:1, preferably 15:1 to 3:1, more preferably 10:1 to 6:1.
  12. 根据权利要求1-11任一项所述的凝胶组合物,其特征在于,所述碱性氨基酸或无机碱以足以部分或完全中和N-长链酰基氨基酸、N-长链酰基氨基酸二肽的量存在,优选中和度在85%以上且小于100%,更优选中和度在88%以上且小于100%。 The gel composition according to any one of claims 1 to 11, characterized in that the basic amino acid or inorganic base is present in an amount sufficient to partially or completely neutralize the N-long-chain acyl amino acid or N-long-chain acyl amino acid dipeptide, preferably with a neutralization degree of 85% or more and less than 100%, more preferably with a neutralization degree of 88% or more and less than 100%.
  13. 根据权利要求1-12任一项所述的凝胶组合物,其特征在于,组合物中不含或基本不含增稠剂;The gel composition according to any one of claims 1 to 12, characterized in that the composition does not contain or substantially does not contain a thickener;
    和/或,组合物中不含或基本不含氯化钠。And/or, the composition is free or substantially free of sodium chloride.
  14. 根据权利要求13所述的凝胶组合物,其特征在于,所述增稠剂选自纤维素类、粘多糖类、聚乙烯醇类、胶质类、聚丙烯酸钠类、聚乙烯基吡咯烷酮类、乙烯基聚合物类中的一种或多种。The gel composition according to claim 13, characterized in that the thickener is selected from one or more of cellulose, mucopolysaccharides, polyvinyl alcohols, colloids, sodium polyacrylates, polyvinyl pyrrolidones, and vinyl polymers.
  15. 根据权利要求1-14任一项所述的凝胶组合物,其特征在于,按GB/T 13531.1中规定的稀释法,测凝胶组合物的pH值,pH值在4.5以上,优选5以上,更优选5.5以上;且pH值在13以下,优选11以下,更优选10以下。The gel composition according to any one of claims 1 to 14 is characterized in that, when the pH value of the gel composition is measured by the dilution method specified in GB/T 13531.1, the pH value is above 4.5, preferably above 5, more preferably above 5.5; and the pH value is below 13, preferably below 11, more preferably below 10.
  16. 根据权利要求1-15任一项所述的凝胶组合物,其特征在于,组合物形成凝胶后,利用日本RHEOTECH硬度计检测,在荷重2kg、适配器20mmφ、针入速度6cm/min、针入距离10mm的检测条件下,硬度在1.80以下,优选在1.50以下,更优选在1.00以下。The gel composition according to any one of claims 1 to 15, characterized in that after the composition forms a gel, the hardness is tested by a Japanese RHEOTECH hardness tester under the test conditions of a load of 2 kg, an adapter of 20 mmφ, a needle penetration speed of 6 cm/min, and a needle penetration distance of 10 mm, and is below 1.80, preferably below 1.50, and more preferably below 1.00.
  17. 根据权利要求1-16任一项所述的凝胶组合物,其特征在于,组合物进一步包含水溶性油脂和/或烷基糖苷。The gel composition according to any one of claims 1 to 16, characterized in that the composition further comprises water-soluble oils and/or alkyl glycosides.
  18. 根据权利要求17所述的凝胶组合物,其特征在于,所述水溶性油脂选自PEG橄榄油酯类、PEG异硬脂酸酯类、PEG椰油基酯类、PEG鳄梨酯类中的一种或多种;优选PEG-10橄榄油甘油酯类、橄榄油PEG-7酯类、橄榄油PEG-8酯类、PEG-7橄榄油酸酯、PEG-15甘油异硬脂酸酯、PEG-9椰油基甘油酯类、PEG-11鳄梨甘油酯类中的一种或多种。The gel composition according to claim 17, characterized in that the water-soluble oil is selected from one or more of PEG olive oil esters, PEG isostearates, PEG coconut oil esters, and PEG avocado esters; preferably one or more of PEG-10 olive oil glycerides, olive oil PEG-7 esters, olive oil PEG-8 esters, PEG-7 olive oil esters, PEG-15 glyceryl isostearate, PEG-9 coconut oil glycerides, and PEG-11 avocado glycerides.
  19. 一种凝胶,其特征在于,基于N-长链酰基氨基酸、碱性氨基酸的自增稠形成;A gel characterized by being formed by self-thickening based on N-long-chain acylamino acids and basic amino acids;
    或者,基于N-长链酰基氨基酸、碱性氨基酸、N-长链酰基氨基酸二肽的自增稠形成;Alternatively, the self-thickening formation is based on N-long chain acyl amino acids, basic amino acids, and N-long chain acyl amino acid dipeptides;
    或者,基于N-长链酰基氨基酸、无机碱的自增稠形成;Alternatively, it is formed by self-thickening based on N-long-chain acylamino acids and inorganic bases;
    或者,基于N-长链酰基氨基酸、无机碱、N-长链酰基氨基酸二肽的自增稠形成。 Alternatively, it can be formed by self-thickening based on N-long chain acyl amino acids, inorganic bases, or N-long chain acyl amino acid dipeptides.
  20. 一种凝胶,其特征在于,由权利要求1-18任一项所述的凝胶组合物制备得到。A gel, characterized in that it is prepared from the gel composition according to any one of claims 1 to 18.
  21. 根据权利要求19或20所述的凝胶,其特征在于,凝胶在40±1℃保持24h,恢复室温后可正常使用;The gel according to claim 19 or 20, characterized in that the gel is kept at 40±1°C for 24 hours and can be used normally after returning to room temperature;
    和/或,凝胶在-8±2℃保持24h,恢复室温后可正常使用。And/or, the gel is kept at -8±2°C for 24 hours and can be used normally after returning to room temperature.
  22. 根据权利要求19-21任一项所述的凝胶,其特征在于,所述凝胶为清洁凝胶、护肤凝胶、洗发凝胶、沐浴凝胶、剃须凝胶、卸妆凝胶、按摩凝胶、化妆用凝胶、口腔用凝胶或多功能凝胶。The gel according to any one of claims 19 to 21, characterized in that the gel is a cleaning gel, a skin care gel, a shampoo gel, a shower gel, a shaving gel, a makeup remover gel, a massage gel, a cosmetic gel, an oral gel or a multifunctional gel.
  23. 一种权利要求1-18任一项所述的凝胶组合物的用途,其特征在于,用于清洁组合物、洗涤组合物、化妆品组合物、皮肤护理组合物或口腔护理组合物。Use of the gel composition according to any one of claims 1 to 18, characterized in that it is used in a cleaning composition, a washing composition, a cosmetic composition, a skin care composition or an oral care composition.
  24. 一种牙膏,其特征在于,含有权利要求1-18任一项所述的凝胶组合物。A toothpaste, characterized in that it contains the gel composition according to any one of claims 1 to 18.
  25. 一种化妆品,其特征在于,含有权利要求1-18任一项所述的凝胶组合物。A cosmetic, characterized in that it contains the gel composition according to any one of claims 1 to 18.
  26. 一种清洁产品,其特征在于,含有权利要求1-18任一项所述的凝胶组合物。A cleaning product, characterized in that it contains the gel composition according to any one of claims 1 to 18.
  27. 一种权利要求1-18任一项所述的凝胶组合物的制备方法,其特征在于,包含如下步骤:A method for preparing the gel composition according to any one of claims 1 to 18, characterized in that it comprises the following steps:
    在75-90℃,优选80-85℃条件下,混合组分(a)N-长链酰基氨基酸、(b)碱性氨基酸或(e)无机碱、(c)水和任选的(d)N-长链酰基氨基酸二肽;Mixing components (a) N-long-chain acyl amino acid, (b) basic amino acid or (e) inorganic base, (c) water and optionally (d) N-long-chain acyl amino acid dipeptide at 75-90° C., preferably 80-85° C.;
    优选的,先将组分(b)或(e)与(c)混合得到溶液I,之后在75-90℃、优选80-85℃条件下使得(a)和任选的(d)熔融得到溶液II,最后,在75-90℃、优选80-85℃条件下,将溶液I与溶液II混合。Preferably, components (b) or (e) and (c) are first mixed to obtain solution I, and then (a) and optional (d) are melted at 75-90°C, preferably 80-85°C to obtain solution II. Finally, solution I is mixed with solution II at 75-90°C, preferably 80-85°C.
  28. 一种赋予清洁组合物凝胶特性的方法,其特征在于,清洁组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上;碱性氨基酸重量百分含量在15wt%以上,优选17wt%以上,更优选 20wt%以上;A method for imparting gel properties to a cleaning composition, characterized in that the cleaning composition comprises (a) an N-long chain acyl amino acid, and (b) a basic amino acid, wherein the weight percentage of the N-long chain acyl amino acid is greater than 30 wt %, preferably greater than 33 wt %, and more preferably greater than 35 wt %; the weight percentage of the basic amino acid is greater than 15 wt %, preferably greater than 17 wt %, and more preferably greater than 18 wt %. 20wt% or more;
    或者,清洁组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在20wt%以上,优选23wt%以上,更优选25wt%以上,碱性氨基酸重量百分含量在10wt%以上,优选12wt%以上,更优选14wt%以上;Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid, (b) a basic amino acid, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 20 wt %, preferably greater than 23 wt %, more preferably greater than 25 wt %, and the weight percentage of the basic amino acid is greater than 10 wt %, preferably greater than 12 wt %, more preferably greater than 14 wt %;
    或者,清洁组合物包含(a)N-长链酰基氨基酸,(b)碱性氨基酸,其中,N-长链酰基氨基酸重量百分含量在20wt%以上,优选23wt%以上,更优选25wt%以上,N-长链酰基氨基酸与碱性氨基酸的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid and (b) a basic amino acid, wherein the weight percentage of the N-long-chain acyl amino acid is above 20 wt %, preferably above 23 wt %, more preferably above 25 wt %, and the molar ratio of the N-long-chain acyl amino acid to the basic amino acid is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
  29. 一种赋予清洁组合物凝胶特性的方法,其特征在于,清洁组合物包含(a)N-长链酰基氨基酸,(e)无机碱,其中,N-长链酰基氨基酸重量百分含量在40wt%以上,优选43wt%以上,更优选45wt%以上,无机碱重量百分含量在5.5wt%以上,优选6wt%以上,更优选6.5wt%以上;A method for imparting gel properties to a cleaning composition, characterized in that the cleaning composition comprises (a) an N-long-chain acylamino acid, and (e) an inorganic base, wherein the weight percentage of the N-long-chain acylamino acid is greater than 40 wt%, preferably greater than 43 wt%, more preferably greater than 45 wt%, and the weight percentage of the inorganic base is greater than 5.5 wt%, preferably greater than 6 wt%, more preferably greater than 6.5 wt%;
    或者,清洁组合物包含(a)N-长链酰基氨基酸,(e)无机碱,(d)N-长链酰基氨基酸二肽,其中,N-长链酰基氨基酸与N-长链酰基氨基酸二肽的重量百分含量总和在30wt%以上,优选33wt%以上,更优选35wt%以上,无机碱重量百分含量在4wt%以上,优选4.5wt%以上,更优选5wt%以上;Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid, (e) an inorganic base, and (d) an N-long-chain acyl amino acid dipeptide, wherein the total weight percentage of the N-long-chain acyl amino acid and the N-long-chain acyl amino acid dipeptide is greater than 30 wt %, preferably greater than 33 wt %, more preferably greater than 35 wt %, and the weight percentage of the inorganic base is greater than 4 wt %, preferably greater than 4.5 wt %, more preferably greater than 5 wt %;
    或者,清洁组合物包含(a)N-长链酰基氨基酸,(e)无机碱,其中,N-长链酰基氨基酸重量百分含量在30wt%以上,优选33wt%以上,更优选35wt%以上,N-长链酰基氨基酸与无机碱的摩尔比为1:0.98至1:0.85,优选1:0.96至1:0.88,更优选1:0.95至1:0.90。 Alternatively, the cleaning composition comprises (a) an N-long-chain acyl amino acid and (e) an inorganic base, wherein the weight percentage of the N-long-chain acyl amino acid is above 30 wt %, preferably above 33 wt %, more preferably above 35 wt %, and the molar ratio of the N-long-chain acyl amino acid to the inorganic base is 1:0.98 to 1:0.85, preferably 1:0.96 to 1:0.88, more preferably 1:0.95 to 1:0.90.
PCT/CN2023/120158 2022-10-13 2023-09-20 Gel composition, and preparation and use thereof WO2024078286A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003097005A1 (en) * 2002-05-16 2003-11-27 Beiersdorf Ag Highly foaming cleansing gel containing acylamino acid surfactants
CN1798821A (en) * 2003-04-01 2006-07-05 味之素株式会社 Gel composition
JP2008222759A (en) * 2007-03-09 2008-09-25 Shinshu Univ Gelling agent
CN102988243A (en) * 2012-12-21 2013-03-27 宁波御坊堂生物科技有限公司 Face cleaning crystal hard gel and preparation method thereof
CN104105686A (en) * 2012-02-09 2014-10-15 味之素株式会社 Basic amino acid derivative

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003097005A1 (en) * 2002-05-16 2003-11-27 Beiersdorf Ag Highly foaming cleansing gel containing acylamino acid surfactants
CN1798821A (en) * 2003-04-01 2006-07-05 味之素株式会社 Gel composition
JP2008222759A (en) * 2007-03-09 2008-09-25 Shinshu Univ Gelling agent
CN104105686A (en) * 2012-02-09 2014-10-15 味之素株式会社 Basic amino acid derivative
CN102988243A (en) * 2012-12-21 2013-03-27 宁波御坊堂生物科技有限公司 Face cleaning crystal hard gel and preparation method thereof

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